Processes for Introduction of Liquid Activators in Olefin Polymerization Reactions

ABSTRACT

The present disclosure provides methods and systems for introducing an activator to a polymerization reactor. The methods may include introducing liquid activator to a mixing vessel or an inline mixer and mixing aliphatic hydrocarbon solvent to form an activator solution which is introduced to a polymerization reactor. The systems may include a storage vessel, a mixing vessel or inline mixer configured to mix a liquid activator with a hydrocarbon solvent, and a polymerization reactor. The present disclosure also provides a process for producing a polyolefin. The process may include introducing liquid activator to an inline mixer and mixing an aliphatic hydrocarbon solvent with the liquid activator to form an activator solution. The process may include introducing the activator solution, a catalyst, and an olefin feed to a polymerization reactor.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Ser. No. 62/946,594, filed Dec.11, 2019, herein incorporated by reference.

FIELD

The present disclosure provides processes and systems for introductionof liquid activators to olefin polymerization reactors.

BACKGROUND

Polyolefins are widely used commercially because of their robustphysical properties. Polyolefins are typically prepared with anactivated catalyst that polymerizes olefin monomers. Catalysts forolefin polymerization are often based on metallocenes as catalystprecursors, which are activated either with an alumoxane or an activatorcontaining a non-coordinating anion. A non-coordinating anion, iscapable of stabilizing the resulting metal cation of the catalyst.Because such activators are fully ionized and the corresponding anion ishighly non-coordinating, such activators can be effective as olefinpolymerization catalyst activators. However, because they are ionicsalts, such activators are typically insoluble in aliphatic hydrocarbonsand only sparingly soluble in aromatic hydrocarbons. The insolubility orpartial solubility of previous activators leads to inaccuracies inmeasuring quantities and also develops a need to pre-mix activators andcatalysts using complicated systems with various mixing and holdingvessels in order to provide activated catalyst to olefin polymerizationreactors.

Furthermore, it is desirable to conduct most polymerizations ofα-olefins in aliphatic hydrocarbon solvents due to the compatibility ofsuch solvents with the olefin monomer and in order to reduce thearomatic hydrocarbon content of the resulting polymer product.Typically, ionic salt activators are added to such polymerizations inthe form of a solution in an aromatic solvent such as toluene. The useof even a small quantity of such an aromatic solvent to introduce theactivator into the polymerization reactor can be undesirable since thearomatic solvent is removed in a post-polymerization devolatilizationstep and separated from other volatile components, which is a processthat adds significant cost and complexity to commercial production ofpolyolefins. Additionally, activators may exist in the form of a solid,or an oily, intractable material which is not readily handled andmetered or precisely incorporated into the reaction mixture. Thereremains a need for methods of providing for introduction of liquidactivators to olefin polymerization reactors.

Another problem with previously designed systems for dispensing andpremixing activators is that these systems are unnecessarily complex andcostly, both in installation and operation. Available systems arevoluminous and cumbersome, and may involve several tanks for storing anddiluting activator or the combination of activator and catalyst. Inaddition, the use of large vessels and large amounts of diluent forpreparing catalyst and activator slurries increases initial costs andgreatly increases the costs associated with devolatilization ofpolyolefin products.

There is a need for improved processes allowing for measurement in theuse and introduction of liquid activators to olefin polymerizationreactors.

SUMMARY

The present disclosure provides a method for introducing an activator toa polymerization reactor including introducing an amount of liquidactivator to a mixing vessel. The method includes mixing an aliphatichydrocarbon solvent with the liquid activator in the mixing vessel toform an activator solution. The method includes introducing theactivator solution to a polymerization reactor.

The present disclosure also provides a method for introducing anactivator to a polymerization reactor including introducing an amount ofliquid activator to an inline mixer. The method includes mixing analiphatic hydrocarbon solvent with the liquid activator in the inlinemixer to form an activator solution. The method includes introducing theactivator solution to a polymerization reactor.

Additionally, the present disclosure provides a system for introducingan activator to a polymerization reactor including a storage vessel anda mixing vessel configured to mix a liquid activator and aliphatichydrocarbon solvent. The mixing vessel is coupled with the storagevessel, and a polymerization reactor is coupled with the mixing vessel.

Furthermore, the present disclosure provides a system for introducing anactivator to a polymerization reactor including a storage vessel and aninline mixer configured to mix a liquid activator and aliphatichydrocarbon solvent. The inline mixer is coupled with the storagevessel, and a polymerization reactor fluidly connected with the inlinemixer.

The present disclosure also provides a method for introducing anactivator to a polymerization reactor including introducing an amount ofaliphatic hydrocarbon solvent to an amount of liquid activator in avessel to form an activator solution. The method includes introducingthe activator solution to a polymerization reactor.

The present disclosure provides a process for producing a polyolefin,the process including introducing an amount of liquid activator to aninline mixer and mixing an aliphatic hydrocarbon solvent with the liquidactivator in the inline mixer to form an activator solution. The methodincludes introducing the activator solution, a catalyst, and an olefinfeed to a polymerization reactor.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a diagram of an apparatus for introduction of activator to anolefin polymerization reactor according to an embodiment.

FIG. 2 is a diagram of an apparatus for introduction of activator to anolefin polymerization reactor according to an embodiment.

FIG. 3 is a diagram of an apparatus for introduction of activator to anolefin polymerization reactor according to an embodiment.

FIG. 4 is a diagram of an apparatus for introduction of activator to anolefin polymerization reactor according to an embodiment.

DETAILED DESCRIPTION

A “storage tank” is a vessel capable of retaining liquids that is or canbe made to be nonreactive to activators. A storage tank may includetemperature control, pressure control, and/or inert gas purge.

An “inert gas” is a gas which is unreactive an olefin polymerizationprocess, and includes Helium, Nitrogen, Neon, Argon, Krypton, and C₂-C₆saturated hydrocarbons, such as ethane, propane, butane, isobutane,isopentane, neopentane, and/or hexane.

An “aliphatic hydrocarbon” is a compound containing carbon and hydrogenjoined together in straight chains, branched chains, and/or non-aromaticrings.

A “liquid” is a compound that is a liquid (in the absence of additionalsolvent) at room temperature (20° C.) at a pressure of 1 atmosphere.

A “flowmeter” is an instrument capable of measuring the rate of flow ofa fluid and may be used to measure the flow through a connecting pipe orline.

A “metering valve” is a valve with variable positioning and control thatis capable of regulating the flow of a fluid, such as needle valves, orother valves containing one or more of (i) a fine annular gap; (ii) ahelical coiled cross section; and/or (iii) a sinter or felt insert. Ametering valve may regulate the flow of fluid automatically or manuallyand may include hydraulic, pneumatic, and solenoid style valves.

A “mixing vessel” is a vessel capable of batch mixing activator andhydrocarbon solvent, may simply be a storage tank, or may includeinternal or external agitation including motorized rotation of blenders,baffles, the tank itself. A mixing vessel may also include temperaturecontrol, pressure control, and/or an inert gas purge.

An “inline mixer” is a vessel or pipe capable of flow through mixing andmay include static or non-static mixing, for example, an inline mixermay include baffles, flow division, radial, plate type, liquid whistle,V blender, static paddle blender or other static mixers and may includenon-static inline mixers such as ribbon blenders, V blenders, or paddleblenders.

A “pump” is a device using pressure to move fluids, and specificallyincludes metering pumps designed to provide specific flow rates, such aspiston pumps or double piston pumps that may provide near constant flowrates in a wide array of discharge pressures.

A “pump station” includes one or more pumps and a flowmeter; theflowmeter may be included in the one or more pumps or as a separatedevice.

A “charge vessel” is a vessel where activator solution may be storedbefore being introduced to the reactor, including storage tanks, mixingvessels, or other vessels.

The terms “cocatalyst” and “activator” are used interchangeably and aredefined to be a compound, including an NCA, which can activate acatalyst compounds of the present disclosure by converting the neutralcatalyst compound to a catalytically active catalyst compound cation.

“Noncoordinating anion” (NCA) means an anion either that does notcoordinate to the catalyst metal cation or that does coordinate to themetal cation, but only weakly. The term NCA is also defined to includemulticomponent NCA-containing activators, such asN,N-dioctadecylanilinium tetrakis(perfluoronaphthyl)borate orN,N-isotridecylanilinium tetrakis(perfluoronaphthyl)borate, that containan acidic cationic group and the non-coordinating anion. The term NCA isalso defined to include neutral Lewis acids, such astris(pentafluoronaphthyl)boron, that can react with a catalyst to forman activated species by abstraction of an anionic group. An NCAcoordinates weakly enough that a neutral Lewis base, such as anolefinically or acetylenically unsaturated monomer can displace the NCAfrom the catalyst center. A metal or metalloid that can form acompatible, weakly coordinating complex may be used or contained in thenoncoordinating anion. Suitable metals can include aluminum, gold, andplatinum. Suitable metalloids can include boron, aluminum, phosphorus,and silicon. The term non-coordinating anion activator includes neutralactivators, ionic activators, and Lewis acid activators.

“Compatible” non-coordinating anions can be those which are not degradedto neutrality when the initially formed complex decomposes. Further, theanion will not transfer an anionic substituent or fragment to the cationso as to cause the combination of cation and substituent or fragment toform a neutral transition metal compound and a neutral by-product fromthe anion. Non-coordinating anions useful in accordance with the presentdisclosure are those that are compatible, stabilize the transition metalcation in the sense of balancing its ionic charge at +1, and yet retainsufficient lability to permit displacement during polymerization.

Description

The present disclosure relates to processes for the introduction ofactivator compounds that can be used in olefin polymerization processes.For example, the present disclosure provides processes for mixing andintroducing activators to a polymerization reactor. In the presentdisclosure, activators have ammonium or phosphonium groups withlong-chain aliphatic hydrocarbyl groups for improved solubility of theactivator in aliphatic solvents, as compared to conventional activatorcompounds.

The present disclosure provides measurement, mixing, and introduction ofactivators, including ammonium borate activators. In the presentdisclosure, activators are described that feature ammonium groups withlong-chain aliphatic hydrocarbyl groups for improved solubility of theactivator in aliphatic solvents, as compared to conventional activatorcompounds. It has been discovered that systems and processes forintroduction of liquid activators of the present disclosure may provideintroduction of quantities of activators and also may decrease capitalexpenditures, decrease operating and maintenance expenditures, whencompared to conventional systems and processes.

Processes and Systems for Measurement, Mixing, and Introduction ofActivators

The activator compounds further illustrated below may be stored in astorage tank as substantially pure liquids or dissolved in hydrocarbonsolvent(s), such as aliphatic hydrocarbons, at a known concentration, an“activator solution.” Because the activators are liquid they may bemeasured using measurement techniques for liquids including the use offlowmeters to measure the quantity of liquid added or removed from astorage tank. Previous activators were not accurately measureable insuch a manner because they were either solids or oily, intractablematerials not readily handled, measured, or metered. Additionally,because the activators are substantially pure liquids, the density canbe determined and the flow determined by weight change.

The activators may be dissolved in hydrocarbon solvent at a knownconcentration in a storage tank, a mixing tank, or inline mixer.Dissolution may be accomplished by determination of the flow or weightof activator and adding the appropriate amount of hydrocarbon solvent.Suitable hydrocarbon solvents include aliphatic and aromatichydrocarbons. While aromatic hydrocarbon are suitable solvents, theiruse may be reduced or eliminated because the production of polyolefinsfree of aromatic hydrocarbons increases the value of the polymer anddecreases cost of polymer devolatilization. Suitable hydrocarbonsolvents include non-coordinating, inert liquids. Examples ofdiluents/solvents for polymerization may include straight andbranched-chain hydrocarbons, such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof, such as can be found commercially (Isopar™); perhalogenatedhydrocarbons, such as perfluorinated C₄ to C₁₀ alkanes, chlorobenzene,and aromatic and alkylsubstituted aromatic compounds, such as benzene,toluene, mesitylene, and xylene. Suitable solvents may also includeliquid olefins which may act as monomers or comonomers includingethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In atleast one embodiment, aliphatic hydrocarbon solvents are used as thesolvent, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof. In anotherembodiment, the solvent is not aromatic, such as aromatics are presentin the solvent at less than 1 wt %, such as less than 0.5 wt %, such asless than 0.1 wt % based upon the combined weight of solvents present.

The systems of the present disclosure may include a storage tanksuitable for storage of liquid activator or an activator solution. In atleast one embodiment, the activator storage tank is fluidly connected toa polymerization reactor. In another embodiment, the activator storagetank is fluidly connected with a pump station fluidly connected to apolymerization reactor. It may be advantageous to allow for dilution ofthe activator or activator solution to allow for precise introduction ofsmall quantities of activator to the polymerization reactor. Dilutionmay occur in a mixing vessel, an inline mixer, a charge vessel, ordirect dilution of activator in a storage tank.

FIG. 1 is a flow diagram of an example apparatus 100 for introduction ofliquid activator into an olefin polymerization reactor. As shown in FIG.1, the liquid activator may be stored in storage tank 104, which may bepressurized by inert gas line 102. Pressures in storage tank 104 may befrom about 150 kPa to about 1500 kPa, such as about 800 kPa to about1000 kPa. The activator may exit storage tank 104 via line 106 and beintroduced to first optional pump 108. The activator, via line 110, maybe combined with hydrocarbon solvent, such as aliphatic hydrocarbon, vialine 112 in mixing vessel 114 forming an activator solution.Alternatively, a solution of liquid activator in hydrocarbon solvent maybe stored in storage tank 104 and addition of hydrocarbon solvent, suchas aliphatic hydrocarbon, via line 112 serves to dilute the activatorsolution to a second concentration. Lines 106 or 110 may contain aflowmeter (not shown) and/or metering valves (not shown) to measureand/or dispense the amount of activator entering mixing vessel 114.Similarly, line 112 may include a flowmeter (not shown) and/or meteringvalve (not shown) to measure and/or dispense an amount of hydrocarbonsolvent to mixing vessel 114. The concentration of activator in theactivator solution may be known in the mixing vessel, samples may betaken from mixing vessel 114 or from other points in the system todetermine concentration of activator in the activator solution. Theactivator solution may have a molarity of about 0.1 mM to 100 mM, suchas 30 mM to 50 mM. The activator solution may exit mixing vessel 114through line 116 to second optional pump 118 and then be introduced vialine 120 to charge vessel 122.

Charge vessel 122 may be used as a holding tank for activator solutionto be used in polymerization reactions. Charge vessel 122 may be anysuitable charge vessel and the activator solution may exit charge vessel122 via line 124 and be introduced to pump station 126. Pump station 126may be designed to pump amounts of activator solution via line 128 topolymerization reactor 130. For example pump station 126 may includeadjustable membrane pumps that allow for transfer of activator solutionat a controllable flow rate. For example, suitable flow rates ofactivator solutions may include 0.1 L/h to 500 l/h, such as 30 L/h to 50L/h. Other reactants, reagents, and materials may enter polymerizationreactor 130 through additional inlet lines, such as line 132. Forexample, catalysts, co-catalyst, scavengers, co-activators, olefins,inert gases, support material, and other additives may all be added topolymerization reactor 130 through additional inlet lines. Additionally,the polymerization reactor may have one or more outlet lines for removalof products, by-products, or reagents, such as overhead line 134 andbottoms line 136.

FIG. 2 is a flow diagram of an example apparatus 200 for introduction ofliquid activator into an olefin polymerization reactor, according toanother embodiment. As shown in FIG. 2, the liquid activator may bestored in storage tank 204, which may be pressurized by inert gas line202. Pressures in storage tank 204 may be from about 150 kPa to about1500 kPa, such as about 800 kPa to about 1000 kPa. The activator mayexit storage tank 204 via line 206 to first optional pump 208. Theactivator via line 210 may be combined with hydrocarbon solvent, such asaliphatic hydrocarbon, via line 212 in mixing vessel 214 forming anactivator solution. Line 206 or line 210 may contain a flowmeter (notshown) and/or metering valves (not shown) to measure and/or dispense theamount of activator entering mixing vessel 214. Similarly, line 212 mayinclude a flowmeter (not shown) and/or metering valve (not shown) tomeasure and/or dispense the amount of hydrocarbon solvent enteringmixing vessel 214. The concentration of activator in the activatorsolution may be known in the mixing vessel, samples may be taken frommixing vessel 214 or from other points in the system to determineconcentration of activator. The activator solution may have a molarityof about 0.1 mM to 100 mM, such as 30 mM to 50 mM. The activatorsolution may exit mixing vessel 214 through line 216 and be introducedto pump station 218. Pump station 218 may be designed to pump amounts ofactivator solution via line 220 to polymerization reactor 222. Forexample, pump station 218 may include adjustable membrane pumps thatallow for introduction of activator solution at a controllable flowrate. For example, suitable flow rates of activator solutions mayinclude 0.1 L/h to 500 l/h, such as 30 L/h to 50 L/h. Other reactants,reagents, and materials may enter polymerization reactor 222 throughadditional inlet lines, such as line 224. For example, catalysts,co-catalyst, scavengers, co-activators, olefins, inert gases, supportmaterial, and other additives may all be added to polymerization reactor222 through additional inlet lines. Additionally, the polymerizationreactor may have one or more outlet lines for removal of products,by-products, or reagents, such as overhead line 226 and bottoms line228.

FIG. 3 is a flow diagram of an example apparatus 300 for introduction ofliquid activator into an olefin polymerization reactor, according toanother embodiment. As shown in FIG. 3, the liquid activator may bestored in storage tank 304, which may be pressurized by inert gas line302. Pressures in storage tank 304 may be from about 150 kPa to about1500 kPa, such as about 800 kPa to about 1000 kPa. The activator mayexit storage tank 304 via line 306 to first optional pump 308. Theactivator via line 310 may be combined with hydrocarbon solvent, such asaliphatic hydrocarbon, via line 312 in inline mixer 314 to form anactivator solution. Line 306 or line 310 may contain a flowmeter (notshown) and/or metering valves (not shown) to measure and/or dispense theamount of activator entering inline mixer 314. Similarly, line 312 mayinclude a flowmeter (not shown) and/or metering valve (not shown) tomeasure and/or dispense the amount of hydrocarbon solvent enteringinline mixer 314. The activator solution may exit inline mixer 314through line 316 and be introduced to mixing vessel 318. Theconcentration of activator in the activator solution may be known in themixing vessel, samples may be taken from mixing vessel 318 or from otherpoints in the system to determine concentration of activator. Theactivator solution may have a molarity of about 0.1 mM to 100 mM, suchas 30 mM to 50 mM. The activator solution may exit mixing vessel 318through line 320 and be introduced to pump station 322. Pump station 322may be designed to pump amount(s) of activator solution via line 324 topolymerization reactor 326. For example, pump station 322 may includeadjustable membrane pumps that allow for introduction of activatorsolution at a controllable flow rate. For example, suitable flow ratesof activator solutions may include 0.1 L/h to 500 l/h, such as 30 L/h to50 L/h. Other reactants, reagents, and materials may enterpolymerization reactor 326 through additional inlet lines, such as line328. For example, catalysts, co-catalyst, scavengers, co-activators,olefins, inert gases, support material, and other additives may all beadded to polymerization reactor 326 through additional inlet lines.Additionally, the polymerization reactor may have one or more outletlines for removal of products, by-products, or reagents, such asoverhead line 330 and bottoms line 332.

FIG. 4 is a flow diagram of an example apparatus 400 for introduction ofliquid activator into an olefin polymerization reactor, according toanother embodiment. As shown in FIG. 4, the liquid activator may bestored in storage tank 404, which may be pressurized by inert gas line402. Pressures in storage tank 404 may be from about 150 kPa to about1500 kPa, such as about 800 kPa to about 1000 kPa. The activator mayexit storage tank 404 via line 406 to first optional pump 408. Theactivator via line 410 may be combined with hydrocarbon solvent, such asaliphatic hydrocarbon, via line 412 in an inline mixer 414 to form anactivator solution. The activator solution may have a molarity of about0.1 mM to 100 mM, such as 30 mM to 50 mM. Line 406 or line 410 maycontain a flowmeter (not shown) and/or a metering valve (not shown) tomeasure and/or dispense an amount of activator entering inline mixer414. Similarly, line 412 may include a flowmeter (not shown) and/or ametering valve (not shown) to measure and/or dispense an amount ofhydrocarbon solvent entering inline mixer 414. The activator solutionmay exit inline mixer 414 through line 416 to enter pump station 418.Pump station 418 may be designed to pump amounts of activator solutionvia line 420 to polymerization reactor 422. For example, pump station418 may include adjustable membrane pumps that allow for introduction ofactivator solution at a controllable flow rate. For example, suitableflow rates of activator solutions may include 0.1 L/h to 500 l/h, suchas 30 L/h to 50 L/h. Other reactants, reagents, and materials may enterpolymerization reactor 422 through additional inlet lines, such as line424. For example, catalysts, co-catalyst, scavengers, co-activators,olefins, inert gases, support material, and other additives may all beadded to polymerization reactor 422 through additional inlet lines.Additionally, polymerization reactor may have one or more outlet linesfor removal of products, by-products, or reagents, such as overhead line426 and bottoms line 428.

Activators

The systems and processes of the present disclosure include activators,such as ammonium or phosphonium metallate or metalloid activatorcompounds, including ammonium or phosphonium groups with long-chainaliphatic hydrocarbyl groups combined with metallate or metalloidanions, such as borates or aluminates which are NCAs. Activatorssuitable for use in the systems and processes of the present disclosureinclude NCA activators that are soluble in aliphatic solvent.

In one or more embodiments, a 20 wt % mixture of the compound inn-hexane, isohexane, cyclohexane, methylcyclohexane, or a combinationthereof, forms a clear homogeneous solution at 25° C. In someembodiments, a 30 wt % mixture of the compound in n-hexane, isohexane,cyclohexane, methylcyclohexane, or a combination thereof, forms a clearhomogeneous solution at 25° C.

In some embodiments, an activator has a solubility of more than 10 mM(or more than 20 mM, or more than 50 mM) at 25° C. (stirred 2 hours) inmethylcyclohexane. In some embodiments, an activator has a solubility ofmore than 1 mM (or more than 10 mM, or more than 20 mM) at 25° C.(stirred 2 hours) in isohexane. In some embodiments, an activator has asolubility of more than 10 mM (or more than 20 mM, or more than 50 mM)at 25° C. (stirred 2 hours) in methylcyclohexane and a solubility ofmore than 1 mM (or more than 10 mM, or more than 20 mM) at 25° C.(stirred 2 hours) in isohexane.

Additionally, activators suitable for use in the systems and processesof the present disclosure include NCA activators that are liquid at roomtemperature and have a density of about 0.5 g/ml to about 1 g/ml, suchas about 0.7 g/ml to about 0.9 g/ml.

It is within the scope of the present disclosure to use an ionizingactivator, neutral or ionic. It is also within the scope of the presentdisclosure to use neutral or ionic activators alone or in combinationwith alumoxane or modified alumoxane activators.

Activators suitable for use in the systems and processes of the presentdisclosure may include a cation and an anion together forming activatorcompounds represented by Formula (I) or (AI):

[R¹R²R³EH]⁺[BR⁴R⁵R⁶R⁷]⁻  (I)

[R¹R²R³EH]^(d+)[M^(k+)Q_(n)]^(d−)  (AI)

where:M is a group 13 atom, such as B or Al;d is 1, 2 or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (such as 1, 2,3, or 4); n−k=d;E is nitrogen or phosphorous;M is an element selected from group 13 of the Periodic Table of theElements, such as boron or aluminum;each Q is independently a hydride, bridged or unbridged dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbylradical.each of R¹, R², and R³ is independently hydrogen, C₁-C₄₀ alkyl orC₅-C₅₀-aryl, where each of R¹, R², and R³ is independently unsubstitutedor substituted with at least one of halide, C₅-C₅₀ aryl, C₆-C₃₅arylalkyl, C₆-C₃₅ alkylaryl and, in the case of the C₅-C₅₀-aryl, C₁-C₅₀alkyl; where R¹, R², and R³ together comprise 15 or more carbon atoms,such as 18 or more carbon atoms, such as 20 or more carbon atoms, suchas 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30or more carbon atoms, such as 35 or more carbon atoms, such as 40 ormore carbon atoms; andeach of R⁴, R⁵, R⁶, and R⁷ is independently is independently a hydride,bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, or halosubstituted-hydrocarbyl radical.

Both the cation part of formulas (A1) and (I) as well as the anion partthereof, which is an NCA, will be further illustrated below.Combinations of cations and NCAs are suitable to be used as activatorsin the systems and processes of the present disclosure.

Activators—The Cations

The cation component of the activators (such as those of formulas (AI)and (I) above), is a protonated Lewis base that can be capable ofprotonating a moiety, such as an alkyl or aryl, from the transitionmetal compound. Thus, upon release of a neutral leaving group (e.g. analkane resulting from the combination of a proton donated from thecationic component of the activator and an alkyl substituent of thetransition metal compound) transition metal cation results, which is thecatalytically active species.

In at least one embodiment, R¹, R² and R³ together include 20 or morecarbon atoms, such as 21 or more carbon atoms, such as 22 or more carbonatoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms,such as 35 or more carbon atoms, such as 37 or more carbon atoms, suchas 40 or more carbon atoms, such as 45 or more carbon atoms, such as 15to 100 carbon atoms, such as 25 to 75 carbon atoms, such as 38 to 70carbon atoms.

In any embodiment of formula (I) or (AI), each of R¹, R² and R³ mayindependently be selected from:

1) optionally substituted linear alkyls (such as methyl, ethyl,n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl,n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl,n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl,n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, or n-tricontyl);

2) optionally substituted branched alkyls (such as alkyl-butyl,alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl,alkyl-decyl, alkyl-undecyl, alkyl-dodecyl, alkyl-tridecyl,alkyl-butadecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl,alkyl-octadecyl, alkyl-nonadecyl, alkyl-icosyl (including multi-alkylanalogs, i.e, dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl,dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl,dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-butadecyl,dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl,dialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-icosyl, trialkyl-butyl,trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl,trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl,trialkyl-tridecyl, trialkyl-butadecyl, trialkyl-pentadecyl,trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl,trialkyl-nonadecyl, and trialkyl-icosyl, etc.), and isomers thereofwhere each alkyl group is independently a C₁ to C₄₀, (alternately C₂ toC₃₀, alternately C₃ to C₂₀) linear, branched or cyclic alkyl group),such as when the alkyl group is methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, or tricontyl);

3) optionally substituted arylalkyls, such as (methylphenyl,ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl,heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl,dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl,hexadecylphenyl, heptadecylphenyl, octadecylphenyl, nonadecylphenyl,icosylphenyl, henicosylphenyl, docosylphenyl, tricosylphenyl,tetracosylphenyl, pentacosylphenyl, hexacosylphenyl, heptacosylphenyl,octacosylphenyl, nonacosylphenyl, tricontylphenyl,3,5,5-trimethylhexylphenyl, dioctylphenyl, 3,3,5-trimethylhexylphenyl,2,2,3,3,4 pentamethypentylylphenyl, and the like);

4) optionally substituted silyl groups, such as a trialkylsilyl group,where each alkyl is independently an optionally substituted C₁ to C₂alkyl (such as trimethylsilyl, triethylsilyl, tripropylsilyl,tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl,trinonylsilyl, tridecylsilyl, triundecylsilyl, tridodecylsilyl,tri-tridecylsilyl, tri-tetradecylsilyl, tri-pentadecylsilyl,tri-hexadecylsilyl, tri-heptadecylsilyl, tri-octadecylsilyl,tri-nonadecylsilyl, tri-icosylsilyl);

5) optionally substituted alkoxy groups (such as —OR*, where R* is anoptionally substituted C₁ to C₂₀ alkyl or aryl (such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, icosyl, phenyl, alkylphenyl (such as methylphenyl, propyl phenyl, etc.), naphthyl, or anthracenyl);

6) halogens (such as Br or Cl); and

7) halogen containing groups (such as bromomethyl, bromophenyl, and thelike), provided that at least one of R¹, R² and R³ contains a branchedalkyl group.

In at least one embodiment, each of R¹, R², and R³ is independentlyhydrogen, C₁-C₄₀ alkyl or C₅-C₅₀-aryl, where each of R¹, R², and R³ isindependently unsubstituted or substituted with at least one of halide,C₅-C₅₀ aryl, C₆-C₃₅ arylalkyl, C₆-C₃₅ alkylaryl and, in the case of theC₅-C₅₀-aryl, C₁-C₅₀ alkyl.

In at least one embodiment, R¹ and R² are independently C₁-C₂₂-alkyl,substituted C₁-C₂₂-alkyl, unsubstituted phenyl, or substituted phenyl(in at least one embodiment, each of R¹, R² and R³ is independentlyselected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,n-nonadecyl, and n-icosyl);

In some embodiments, R¹ is a C₁-C₂₀ alkyl group (such as a C₁-C₁₀ alkylgroup, a C₁ to C₂ alkyl, or methyl), where R¹ is optionally substitutedand each of R² and R³ is independently an optionally substituted C₁-C₄₀alkyl group or aryl and/or para-substituted phenyl group, where the metaand para substituents are, independently, an optionally substituted C₁to C₄ hydrocarbyl group, an optionally substituted alkoxy group, anoptionally substituted silyl group, a halogen, or a halogen containinggroup.

In some embodiments, a branched alkyl may have 1 to 30 tertiary orquaternary carbons, alternately 2 to 10 tertiary or quaternary carbons,alternately 2 to 4 tertiary or quaternary carbons, alternately thebranched alkyl has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 tertiaryor quaternary carbons.

At Least One Branched R Group

In some embodiments, at least one (alternately one, two or three) of R¹,R², and R³ is a branched alkyl, (such as a C₃-C₄₀ branched alkyl,alternately such as a C₇ to C₄₀ branched alkyl).

In some embodiments, each of R¹, R², and R³ is independently C₁-C₄₀linear or branched alkyl, C₅-C₅₀-aryl (such as C₅ to C₂₂), where each ofR¹, R², and R³ is independently unsubstituted or substituted with atleast one of halide, C₅-C₅₀ aryl, C₆-C₃₅ arylalkyl, C₆-C₃₅ alkylaryland, in the case of the C₅-C₅₀-aryl, C₁-C₅₀ alkyl, provided that atleast one of R¹, R², and R³ is a branched alkyl (such as a C₃-C₄₀branched alkyl), such as at least two of R¹, R², and R³ are a branchedalkyl (such as a C₃-C₄₀ branched alkyl), or each of R¹, R², and R³ is abranched alkyl (such as a C₃-C₄₀ branched alkyl);

In at least one embodiment, each of R¹, R², and R³ is independentlyC₁-C₄₀ linear or branched alkyl, C₅-C₅₀-aryl (such as C₅-C₂₂-aryl, suchas an arylalkyl (where the alkyl has from 1 to 10 carbon atoms and thearyl has from 6 to 20 carbon atoms), or five-, six- or seven-memberedheterocyclyl comprising at least one atom selected from N, P, O and S,where each of R¹ R², and R³ is optionally substituted by halogen, —NR′₂,—OR′ or —SiR′₃ (where R′ is independently hydrogen or C₁-C₂₀hydrocarbyl), where R² optionally bonds with R⁵ to independently form afive-, six- or seven-membered ring, and provided that at least one ofR¹, R², and R³ is a C₃-C₄₀ branched alkyl, alternately at least two ofR¹, R², and R³ are a C₃-C₄₀ branched alkyl.

In some embodiments, R¹ is a C₁-C₄₀ linear alkyl, such as methyl; eachof R², and R³ is independently C₁-C₄₀ linear or branched alkyl,C₅-C₂₂-aryl, C₅ to C₅₀ arylalkyl where the alkyl has from 1 to 30 carbonatoms and the aryl has from 6 to 20 carbon atoms, or five-, six- orseven-membered heterocyclyl comprising at least one atom selected fromN, P, O and S, where each of R¹ R², and R³ is optionally substituted byhalogen, where R² optionally bonds with R⁵ to independently form afive-, six- or seven-membered ring, provided that at least one of R²,and R³ is a C₃-C₄₀ branched alkyl, alternately both of R², and R³ are aC₃-C₄₀ branched alkyl, alternately each of R¹, R², and R³ is a C₃-C₄₀branched alkyl.

In one or more embodiments, R¹ is methyl.

In one or more embodiments, R² is unsubstituted phenyl or substitutedphenyl. In at least one embodiment, R² is phenyl, methyl phenyl, n-butylphenyl, n-octadecyl-phenyl, or an isomer thereof, such as R² is meta orpara substituted phenyl, such as meta- or para-substituted alkylsubstituted phenyl.

In any embodiment, R³ is branched alkyl such as isopropyl, isobutyl,isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl,isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl,isohexadecyl, isoheptadecyl, isooctadecyl, isononadecyl, isoicosyl,isohenicosyl, isodocosyl, isotricosyl, isotetracosyl, isopentacosyl,isohexacosyl, isoheptacosyl, isooctacosyl, isononacosyl, orisotricontyl, alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl,alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl,alkyl-tridecyl, alkyl-butadecyl, alkyl-pentadecyl, alkyl-hexadecyl,alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, alkyl-icosyl(including multi-alkyl analogs, i.e, dialkyl-butyl, dialkyl-pentyl,dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl,dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl,dialkyl-butadecyl, dialkyl-pentadecyl, dialkyl-hexadecyl,dialkyl-heptadecyl, dialkyl-octadecyl, dialkyl-nonadecyl,dialkyl-icosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl,trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl,trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl,trialkyl-butadecyl, trialkyl-pentadecyl, trialkyl-hexadecyl,trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, andtrialkyl-icosyl), and isomers thereof where each alkyl group isindependently a C₁ to C₄₀, (alternately C₂ to C₃₀, alternately C₃ toC₂₀) linear, branched or cyclic alkyl group, such as the alkyl group ismethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl,tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, ortricontyl).

In some embodiments, R¹ is methyl; R² is C₆-C₅₀ aryl which is optionallysubstituted with at least one of halide, C₁-C₃₅ alkyl, C₅-C₅ aryl,C₆-C₃₅ arylalkyl, and C₆-C₃₅ alkylaryl; and R³ is C₁-C₄₀ branched alkylwhich is optionally substituted with at least one of halide, C₁-C₃₅alkyl, C₅-C₁₅ aryl, C₆-C₃₅ arylalkyl, and C₆-C₃₅ alkylaryl.

In any embodiment, R¹ is methyl, and R² is phenyl, methyl phenyl,n-butyl phenyl, n-octadecyl-phenyl, or an isomer thereof, such as R² ismeta or para substituted phenyl, such as meta- or para-substituted alkylsubstituted phenyl, and R³ is branched alkyl.

In any embodiment, R¹ is methyl, and R² is branched alkyl, and R³ isbranched alkyl.

In some embodiments, R¹ is methyl, R² is substituted phenyl, R³ is C₁₀to C₃₀ branched alkyl. In at least one such embodiment, R² is not metasubstituted phenyl. In at least one such embodiment, R² is not orthosubstituted phenyl.

In some embodiments, R¹ is methyl, R² is C₁ to C₃₅ alkyl substitutedphenyl (such as ortho- or meta-substituted), R³ is C₈ to C₃₀ branchedalkyl.

In some embodiments, R¹ is C₁ to C₁₀ alkyl, R² is C₁ to C₃₅ alkylsubstituted phenyl (such as para substituted phenyl), R³ is C₈ to C₃₀branched alkyl.

In some embodiments, R¹ is methyl; R² is C₁ to C₃₅ alkyl substitutedphenyl, such as methylphenyl, ethylphenyl, n-propylphenyl,n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl,n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecyl, phenyln-dodecylphenyl, n-tridecylphenyl, n-butadecylphenyl,n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl,n-octadecylphenyl, n-nonadecylphenyl, and n-icosylphenyl,n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl,n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl,n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl,n-triacontylphenyl; and R³ is C₈ to C₃₀ branched alkyl, such asi-propyl, alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl,alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl,alkyl-tridecyl, alkyl-butadecyl, alkyl-pentadecyl, alkyl-hexadecyl,alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, and alkyl-icosyl(such as 2-alkyl-pentyl, 2-alkyl-hexyl, 2-alkyl-heptyl, 2-alkyl-octyl,2-alkyl-nonyl, 2-alkyl-decyl, 2-alkyl-undecyl, 2-alkyl-dodecyl,2-alkyl-tridecyl, 2-alkyl-butadecyl, 2-alkyl-pentadecyl,2-alkyl-hexadecyl, 2-alkyl-heptadecyl, 2-alkyl-octadecyl,2-alkyl-nonadecyl, 2-alkyl-icosyl or a multi-alkyl analogs, i.e,dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl,dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl,dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-butadecyl,dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl,dialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-icosyl, trialkyl-butyl,trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl,trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl,trialkyl-tridecyl, trialkyl-butadecyl, trialkyl-pentadecyl,trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl,trialkyl-nonadecyl, and trialkyl-icosyl, etc.), or an isomer thereofwhere each alkyl group is independently a C₁ to C₄₀, (alternately C₂ toC₃₀, alternately C₃ to C₂₀) linear, branched or cyclic alkyl group),such as the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl,henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, or tricontyl).

No Branched Alkyl R Groups

In some embodiments, each of R¹, R², and R³ is independently C₁-C₄₀linear alkyl, C₅-C₂₂-aryl, arylalkyl (where the alkyl has from 1 to 30(or 1 to 10) carbon atoms and the aryl has from 6 to 20 carbon atoms) orfive-, six- or seven-membered heterocyclyl including at least one atomselected from N, P, O and S, where each of R¹ R², and R³ is optionallysubstituted by halogen, —NR′₂, —OR′ or —SiR′₃ (where each R′ isindependently hydrogen or C₁-C₂₀ hydrocarbyl), where R² optionally bondswith R⁵ to independently form a five-, six- or seven-membered ring.

In at least one embodiment, R¹, R², and R³ are independently substitutedor unsubstituted C₁-C₂₂ linear alkyl, or substituted or unsubstitutedphenyl.

In some embodiments, R¹ is an optionally substituted C₁-C₂₀ (or C₁ toC₁₀, or C₁-C₆, or C₁-C₄, or C₁-C₂, or C₁) linear alkyl group and each ofR² and R³ is independently an optionally substituted C₁-C₄₀ linear alkylgroup (such as a C₆ to C₄₀ linear alkyl group, or a C₁₀ to C₃₀ linearalkyl group) or a meta- and/or para-substituted phenyl group, where themeta and para substituents are, independently, an optionally substitutedC₁ to C₄₀ hydrocarbyl group (such as a C₆ to C₄₀ aryl group or linearalkyl group, a C₁₂ to C₃₀ aryl group or linear alkyl group, or a C₁₀ toC₂₀ aryl group or linear alkyl group), an optionally substituted alkoxygroup, an optionally substituted silyl group, a halogen (Br, Cl, I, F,etc.), or a halogen containing group (such as bromoalkyl or bromoaryl).

In at least one embodiment, each of R¹, R² and R³ is independentlyselected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,n-nonadecyl, and n-icosyl.

In some embodiments, R¹ is a methyl group, R² is C₆-C₅₀ aryl which isoptionally substituted with at least one of halide, C₁-C₃₅ alkyl, C₅-C₁₅aryl, C₆-C₃₅ arylalkyl, and C₆-C₃₅ alkylaryl, and R³ is C₁-C₄₀ linearalkyl or C₅-C₄₂-aryl which is optionally substituted with at least oneof halide, C₁-C₃₅ alkyl, C₅-C₅ aryl, C₆-C₃₅ arylalkyl, and C₆-C₃₅alkylaryl, where R² optionally bonds with R³ to independently form afive-, six- or seven-membered ring.

In some embodiments, R¹ is methyl, R² is a C₁ to C₄₀ linear alkyl group(such as a C₆ to C₄₀ linear alkyl, or C₁₀ to C₃₀ linear alkyl), and R³is a para-substituted phenyl group, where the para substituent is,independently, an optionally substituted C₁ to C₄₀ hydrocarbyl group(such as a C₆ to C₄₀ aryl group or linear alkyl group, a C₁₂ to C₃₀ arylgroup or linear alkyl group, or a C₁₀ to C₂ aryl group or linear alkylgroup), an optionally substituted alkoxy group, an optionallysubstituted silyl group, a halogen, or a halogen containing group.

In some embodiments, R² is unsubstituted phenyl or substituted phenyl.In at least one embodiment, R² is phenyl, methyl phenyl, n-butyl phenyl,n-octadecyl-phenyl, or an isomer thereof, such as R² is meta or parasubstituted phenyl, such as meta- or para-substituted alkyl substitutedphenyl. In at least one embodiment, R³ is independently selected from Cto C₃₀ linear alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl,n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl,n-octadecyl, n-nonadecyl, and n-icosyl.

In some embodiments, the meta and para substituents are, independently,an optionally substituted linear alkyl group (such as n-hexyl, n-heptyl,n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl,n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, orn-tricontyl), an optionally substituted silyl group, such as atrialkylsilyl group, where each alkyl is independently an optionallysubstituted C₁ to C₂₀ alkyl (such as trimethylsilyl, triethylsilyl,tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl,trioctylsilyl, trinonylsilyl, tridecylsilyl, triundecylsilyl,tridodecylsilyl, tri-tridecylsilyl, tri-tetradecylsilyl,tri-pentadecylsilyl, tri-hexadecylsilyl, tri-heptadecylsilyl,tri-octadecylsilyl, tri-nonadecylsilyl, tri-icosylsilyl), or anoptionally substituted alkoxy group (such as —OR*, where R* is anoptionally substituted C₁ to C₂₀ alkyl or aryl (such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, icosyl, phenyl, phenyl alkyl (such as methylphenyl, propyl phenyl, etc.), naphthyl, or anthracenyl), a halogen (suchas Br or Cl) or a halogen containing group (such as bromomethyl,bromophenyl, and the like).

In some embodiments, the meta-substituted phenyl is methylphenyl,ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl,n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl,n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl,n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl,n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl,n-icosylphenyl, n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl,n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl,n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl,n-tricontylphenyl, dimethylphenyl, diethylphenyl, di-n-propylphenyl,di-n-butylphenyl, di-n-pentylphenyl, di-n-hexylphenyl,di-n-heptylphenyl, di-n-octylphenyl, di-n-nonylphenyl, di-n-decylphenyl,di-n-undecylphenyl, di-n-dodecylphenyl, di-n-tridecylphenyl,di-n-tetradecylphenyl, di-n-pentadecylphenyl, di-n-hexadecylphenyl,di-n-heptadecylphenyl, di-n-octadecylphenyl, di-n-nonadecylphenyl,di-n-icosylphenyl, di-n-henicosylphenyl, di-n-docosylphenyl,di-n-tricosylphenyl, di-n-tetracosylphenyl, di-n-pentacosylphenyl,di-n-hexacosylphenyl, di-n-heptacosylphenyl, di-n-octacosylphenyl,di-n-nonacosylphenyl, and di-n-tricontylphenyl. The two metasubstituents may be the same or different.

In some embodiments, the para-substituted phenyl is methylphenyl,ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl,n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl,n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl,n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl,n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl,n-icosylphenyl, n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl,n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl,n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, orn-tricontylphenyl.

In some embodiments, R¹ is methyl, R² is n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, orn-icosyl, and R³ is methylphenyl, ethylphenyl, n-propylphenyl,n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl,n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl,n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl,n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl,n-octadecylphenyl, n-nonadecylphenyl, or n-icosylphenyl.

In at least one embodiment, each of R² and R³ is independently selectedfrom methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl,n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl,n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl,n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl,n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl,n-nonadecylphenyl, and n-icosylphenyl.

In at least one embodiment, R¹ is methyl, R² is substituted phenyl, andR³ is C₁₀ to C₃₀ linear alkyl. In some embodiments, R² is not metasubstituted phenyl.

In at least one embodiment, R¹ is methyl, R² is C₁ to C₃₅ alkylsubstituted phenyl (such as ortho- or meta-substituted), R³ is C₁₀ toC₃₀ linear alkyl.

In at least one embodiment, R¹ is methyl, R² is C₁ to C₃₅ alkylsubstituted phenyl (such as para substituted), and R³ is C₁₀ to C₃₀linear alkyl.

In at least one embodiment, R¹ is methyl; R² is C₁ to C₃₅ alkylsubstituted phenyl, such as methylphenyl, ethylphenyl, n-propylphenyl,n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl,n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecyl, phenyln-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl,n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl,n-octadecylphenyl, n-nonadecylphenyl, and n-icosylphenyl,n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl,n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl,n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl,n-triacontylphenyl; and R³ is C₁₀ to C₃₀ linear alkyl, such as n-decyl,n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl,n-henicosyl, n-docosyl, n-tricosyl; n-tetracosyl, n-pentacosyl;n-hexacosyl; n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl.

In at least one embodiment, R² is C₁ to C₃₅ alkyl substituted phenyl,such as methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl,n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl,n-nonylphenyl, n-decylphenyl, n-undecyl, phenyl n-dodecylphenyl,n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl,n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl,n-nonadecylphenyl, and n-icosylphenyl, n-henicosylphenyl,n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl,n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl,n-octacosylphenyl, n-nonacosylphenyl, n-triacontylphenyl; and R³ is C₁₀to C₃₀ linear alkyl, such as n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl; n-tetracosyl,n-pentacosyl; n-hexacosyl; n-heptacosyl, n-octacosyl, n-nonacosyl,n-triacontyl.

In at least one embodiment of formula (I), R¹ is methyl, R² issubstituted phenyl, R³ is C₁₀ to C₃₀ linear alkyl, and R⁴, R⁵, R⁶, R⁷are perfluoronaphthyl.

In at least one embodiment of formula (AI), R¹ is methyl, R² issubstituted phenyl, R³ is C₁₀ to C₃₀ linear alkyl, E is nitrogen, andeach Q is perfluoronaphthyl.

In at least one embodiment, R¹ is methyl; R² is C₁ to C₃₅ alkylsubstituted phenyl, such as methylphenyl, ethylphenyl, n-propylphenyl,n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl,n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecyl, phenyln-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl,n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl,n-octadecylphenyl, n-nonadecylphenyl, and n-icosylphenyl,n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl,n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl,n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl,n-triacontylphenyl; R³ is C₁₀ to C₃₀ linear alkyl, such as n-decyl,n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl,n-henicosyl, n-docosyl, n-tricosyl; n-tetracosyl, n-pentacosyl;n-hexacosyl; n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl; andeach Q or each of R⁴, R⁵, R⁶, R⁷ are perfluoronaphthyl.

In at least one embodiment, R¹ is o-MePh, R² and R³ are n-octadecyl.

In at least one embodiment, R¹ is m-MePh, R² and R³ are n-octadecyl.

In at least one embodiment, R¹ is not para-alkylphenyl, such as p-MePh.

In at least one embodiment, R¹ is Me, R² is n-octadecylaryl, and R³ isn-octadecyl.

In at least one embodiment, R¹ is Me, R² is n-octadecylphenyl, and R³ isn-octadecyl.

In at least one embodiment, R¹ is Me, R² is n-butylaryl, and R³ isn-octadecyl.

In at least one embodiment, R¹ is Me, R² is n-butylphenyl, and R³ isn-octadecyl.

In at least one embodiment, R¹ is n-decyl, R² is n-butylaryl, and R³ isn-decyl.

In at least one embodiment, R¹ is n-decyl, R² is n-butylphenyl, and R³is n-decyl.

In at least one embodiment, R¹ is n-propyl, R² is p-methylphenyl, and R³is n-octadecyl.

In at least one embodiment, the cation is selected from the groupconsisting of:

In at least one embodiment, R¹ is a methyl group; R² is C₆-C₄₀ aryl(such as substituted phenyl) and R³ is independently C₁-C₃₅ linearalkyl, C₅-C₄₀-aryl, where each of R² and R³ is independentlyunsubstituted or substituted with at least one of C₁-C₃₅alkyl, C₅-C₃₀aryl, C₆-C₃₀₅ arylalkyl, C₆-C₃₀ alkylaryl, halogen, where R² optionallybonds with R³ to independently form a five-, six- or seven-memberedring, where R², and R³ together include 20 or more carbon atoms; andoptionally R¹, R², and R³ together include 21 or more carbon atoms, suchas 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30or more carbon atoms, such as 35 or more carbon atoms, such as 40 ormore carbon atoms. In at least one embodiment, R² is independentlysubstituted C₁-C₂₂-alkyl, unsubstituted phenyl, or substituted phenyl.In at least one embodiment, R³ is independently selected from methyl,ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl,n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl.

In some embodiments, the cation is selected from the group consistingof:

In some embodiments, the compound represented by formulas (A) and (I)includes a cation selected from the group consisting of:

In some embodiments, R¹ is not methyl, R² is not C₁₈ alkyl and R³ is notC₁₈ alkyl, alternately R¹ is not methyl, R² is not C₁₈ alkyl and R³ isnot C₁₈ alkyl and at least one Q is not substituted phenyl, such as allQ are not substituted phenyl.

Activators—The Anion

Suitable activators for use in the systems and processes of the presentdisclosure are non-coordinating anion (NCA) activators. Non-coordinatinganions useful in accordance with the present disclosure are those thatare compatible, stabilize the transition metal cation in the sense ofbalancing its ionic charge at +1, and yet retain sufficient lability topermit displacement during polymerization. Suitable ionizing activatorsmay include an NCA, such as a compatible NCA.

An NCA may include “bulky activators” where the anion is represented bythe formula:

where:each R^(A) is independently a halide, such as a fluoride;each R^(B) is independently a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R^(D), whereR^(D) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (such asR^(B) is a fluoride or a perfluorinated phenyl group);each R^(C) is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl groupor a siloxy group of the formula —O—Si—R^(D), where R^(D) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group (such as R^(D) is a fluoride or aC perfluorinated aromatic hydrocarbyl group); where R^(B) and R^(C) canform one or more saturated or unsaturated, substituted or unsubstitutedrings (such as R^(B) and R^(C) form a perfluorinated phenyl ring);where the anion has a molecular weight of greater than 1,020 g/mol; andwhere at least three of the substituents on the B atom each have amolecular volume of greater than 250 cubic Å, alternately greater than300 cubic Å, or alternately greater than 500 cubic Å.

“Molecular volume” is used as an approximation of spatial steric bulk ofan activator molecule in solution. Comparison of substituents withdiffering molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple ‘Back of theEnvelope’ Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964, which is incorporated by reference.Molecular volume (MV), in units of cubic Å, is calculated using theformula: MV=8.3V_(S), where V_(S) is the scaled volume. V_(S) is the sumof the relative volumes of the constituent atoms, and is calculated fromthe molecular formula of the substituent using the following table ofrelative volumes. For fused rings, the V_(S) is decreased by 7.5% perfused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) shortperiod, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rbto I 7.5 3^(rd) long period, Cs to Bi 9

For a list of suitable non-coordinating anions please see U.S. Pat. No.8,658,556, incorporated by reference.

The anion component of the activators includes those represented by theformula [M^(k+)Q_(n)]⁺ where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6(such as 1, 2, 3, or 4); M is an element selected from Group 13 of thePeriodic Table of the Elements, such as boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 30 carbon atoms.

In some embodiments, each Q is a fluorinated hydrocarbyl group,optionally having 1 to 30 carbon atoms, such as where each Q is afluorinated aryl group, such as where each Q is a perfluorinated arylgroup. In at least one embodiment, at least one Q is not substitutedphenyl, such as perfluorophenyl, such as all Q are not substitutedphenyl, such as perfluorophenyl.

In some embodiments, each Q is independently a hydride, bridged orunbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl, orhalosubstituted-hydrocarbyl radical. In some embodiments, each Q is afluorinated hydrocarbyl group having 1 to 30 carbon atoms, such as eachQ is a fluorinated aryl (such as phenyl or naphthyl) group, aperflourinated aryl (such as phenyl or naphthyl) group. Examples ofsuitable [M^(k+)Q_(n)]^(d−) also include diboron compounds as disclosedin U.S. Pat. No. 5,447,895, incorporated by reference.

In some embodiments, each Q is independently a hydride, bridged orunbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl, orhalosubstituted-hydrocarbyl radical, provided that when Q is afluorophenyl group, then R² is not a C₁-C₄₀ linear alkyl group, such asR² is not an optionally substituted C₁-C₄₀ linear alkyl group(alternately when Q is a substituted phenyl group, then R² is not aC₁-C₄₀ linear alkyl group, such as R² is not an optionally substitutedC₁-C₄₀ linear alkyl group). In some embodiments, when Q is afluorophenyl group (alternately when Q is a substituted phenyl group),then R² is a meta- and/or para-substituted phenyl group, where the metaand para substituents are, independently, an optionally substitutedC₁-C₄₀ hydrocarbyl group (such as a C₆ to C₄₀ aryl group or linear alkylgroup, a C₁₂ to C₃₀ aryl group or linear alkyl group, or a C₁₀ to C₂₀aryl group or linear alkyl group), an optionally substituted alkoxygroup, or an optionally substituted silyl group. In some embodiments,each Q is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms,such as each Q is a fluorinated aryl (such as phenyl or naphthyl) group,or such as each Q is a perflourinated aryl (such as phenyl or naphthyl)group.

In some embodiments, the [M^(k+)Q_(n)]^(d−) anion is a borate anion offormula [BR⁴R⁵R⁶R⁷]⁻.

In some embodiments, each of R⁴, R⁵, R⁶, and R⁷ is independently isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, or halosubstituted-hydrocarbyl radical, such as,each of R⁴, R⁵, R⁶, and R⁷ is independently is a fluorinated hydrocarbylgroup having 1 to 30 carbon atoms, such each Q is a fluorinated aryl(such as phenyl or naphthyl) group (substituted with from one to sevenfluorine atoms), or perflourinated aryl (such as phenyl or naphthyl)group.

In some embodiments, each of R⁴, R⁵, R⁶, and R⁷ is independently each afluorinated hydrocarbyl group having 1 to 30 carbon atoms, such as eachof R⁴, R⁵, R⁶, and R⁷ is independently is a fluorinated aryl (such asphenyl biphenyl, [(C₆H₃(C₆H₅)₂)₄B], or naphthyl) group. In someembodiments, each of R⁴, R⁵, R⁶, and R⁷ is independently is aperflourinated aryl (such as phenyl biphenyl, [(C₆H₃(C₆H₅)₂)₄B], ornaphthyl) group, where at least one of R⁴, R⁵, R⁶, and R⁷ is substitutedwith from one to seven fluorine atoms. In at least one embodiment, eachof R⁴, R⁵, R⁶, and R⁷ is independently aryl (such as naphthyl), where atleast one of R⁴, R⁵, R⁶, and R⁷ is substituted with from one to sevenfluorine atoms. In any embodiment, all of R⁴, R⁵, R⁶, and R⁷ arenaphthyl, where at least one, two, three, or four of R⁴, R⁵, R⁶, and R⁷is/are substituted with one, two, three, four, five, six or sevenfluorine atoms. In at least one embodiment, each of R⁴, R⁵, R⁶, and R⁷is naphthyl, where at least one of R⁴, R⁵, R⁶, and R⁷ is substitutedwith from one to seven fluorine atoms.

In any embodiment, each of R⁴, R⁵, R⁶, and R⁷ is independently phenyl,where at least one of R⁴, R⁵, R⁶, and R⁷ is phenyl substituted with one,two, three, four, or five fluorine atoms. In some embodiments, as atleast one R⁴, R⁵, R⁶, and R⁷ is not substituted phenyl, such as all ofR⁴, R⁵, R⁶, and R⁷ are not substituted phenyl.

In some embodiments, all Q or all of R⁴, R⁵, R⁶, and R⁷ are notperfluoroaryl, such as perfluorophenyl.

In at least one embodiment, R⁴ is independently naphthyl including onefluorine atom, two fluorine atoms, three fluorine atoms, four fluorineatoms, five fluorine atoms, six fluorine atoms, or seven fluorine atoms.

In at least one embodiment, R⁴ is independently naphthyl including onefluorine atom, two fluorine atoms, three fluorine atoms, four fluorineatoms, five fluorine atoms, six fluorine atoms, or seven fluorine atoms,and each of R⁵, R⁶, and R⁷ is independently phenyl including onefluorine atom, two fluorine atoms, three fluorine atoms, four fluorineatoms, or five fluorine atoms or naphthyl including one fluorine atom,two fluorine atoms, three fluorine atoms, four fluorine atoms, fivefluorine atoms, six fluorine atoms, or seven fluorine atoms.

In some embodiments, when R¹ is methyl, R² is C18 and R³ is C18, theneach of R⁴, R⁵, R⁶, and R⁷ is not perfluorophenyl.

In at least one embodiment, the borate activator includestetrakis(heptafluoronaphth-2-yl)borate.

In some embodiments, anions for use in the non-coordinating anionactivators include those represented by:

where:M* is a group 13 atom, such as B or Al, such as B;each R¹¹ is, independently, a halide, such as a fluoride;each R¹² is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group, such as R¹² is a fluoride or a perfluorinated phenylgroup, or a siloxy group of the formula —O—Si—R^(a), where R^(a) is a C₁to C₂₀ hydrocarbyl or hydrocarbylsilyl group;each R¹³ is a halide, a C₆ to C₂₀ substituted aromatic hydrocarbylgroup, such as where R¹³ is a fluoride or a C₆ perfluorinated aromatichydrocarbyl group, or a siloxy group of the formula —O—Si—R^(a), whereR^(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group; where R¹²and R¹³ can form one or more saturated or unsaturated, substituted orunsubstituted rings, such as where R¹² and R¹³ form a perfluorinatedphenyl ring. In some embodiments, the anion has a molecular weight ofgreater than 700 g/mol, and at least three of the substituents on the M*atom each have a molecular volume of greater than 180 cubic Å.

The calculated total molecular volume (MV) of the anion is the sum ofthe MV per substituent, for example, the MV of perfluorophenyl is 183Å³, and the calculated total MV for tetrakis(perfluorophenyl)borate isfour times 183 Å³, or 732 Å³.

Exemplary suitable anions and their respective scaled volumes andmolecular volumes are shown in Table 2 below. The dashed bonds indicatebonding to boron.

TABLE 2 Molecular MV Calculated Formula Per Total of Each subst. MV IonStructure of Boron Substituents Substituent V_(s) (Å³) (Å³)tetrakis(perfluorophenyl) borate

C₆F₅ 22 183 732 tris(perfluorophenyl)- (perfluoronaphthyl)borate

C₆F₅ C₁₀F₇ 22 34 183 261 810 (perfluorophenyl)tris-(perfluoronaphthyl)borate

C₆F₅ C₁₀F₇ 22 34 183 261 966 tetrakis(perfluoronaphthyl) borate

C₁₀F₇ 34 261 1044 tetrakis(perfluorobiphenyl) borate

C₁₂F₉ 42 349 1396 [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 62 515 2060

The activators may be added to a polymerization in the form of an ionpair using, for example, [M2HTH]+[NCA]− in which the di(hydrogenatedtallow)methylamine (“M2HTH”) cation or [DEBAH]+[NCA]− in which the4-butyl-N,N-bis(isotridecyl)benzenaminium-(“DEBAH”) cation reacts with abasic leaving group on the transition metal complex to form a transitionmetal complex cation and [NCA]−. Alternatively, the transition metalcomplex may be reacted with a neutral NCA precursor, such as B(C₁₀F₇)₃,which abstracts an anionic group from the complex to form an activatedspecies.

In at least one embodiment, the activators obtained in their salt formused for a borate activator compound are: Lithiumtetrakis(heptafluoronaphthalen-2-yl)borate etherate (Li-BF28),N,N-Dimethylanilinium tetrakis(heptafluoronaphthalen-2-yl)borate(DMAH-BF28), Sodium tetrakis(heptafluoronaphthalen-2-yl)borate (Na-BF28)and N,N-dimethylaniliniumtetrakis(heptafluoronaphthalen-2-yl)borate(DMAH-BF28).

In at least one embodiment, an activator of the present disclosure, whencombined with a group 4 metallocene catalyst compound to form an activeolefin polymerization catalyst, produces a higher molecular weightpolymer (e.g., Mw) than comparative activators that use other borateanions.

In at least one embodiment, an activator of the present disclosure whereR¹ is methyl, when combined with a group 4 metallocene to form an activeolefin polymerization catalyst, produces a higher molecular weightpolymer (e.g., Mw) than comparative activators that use other borateanions.

The typical activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is about a 1:1 molar ratio. In someembodiments, NCA activators to catalyst ratios may include from 0.1:1 to100:1, from 0.5:1 to 200:1, from 1:1 to 500:1, or from 1:1 to 1000:1,such as from 0.5:1 to 10:1, or 1:1 to 5:1.

It is also within the scope of the present disclosure that the catalystcompounds can be combined with combinations of alumoxanes and theactivators.

Optional Scavengers or Co-Activators

In addition to these activator compounds, scavengers or co-activatorsmay be introduced to the polymerization reactor in the systems andprocesses of the present disclosure. Aluminum alkyl or organoaluminumcompounds which may be utilized as scavengers or co-activators include,for example, trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.

In at least one embodiment, little or no scavenger is introduced to thepolymerization reactor. Scavenger (such as trialkyl aluminum) can bepresent at 0 mol %, alternately the scavenger is present at a molarratio of scavenger metal to transition metal of less than 100:1, such asless than 50:1, such as less than 15:1, such as less than 10:1.

Catalyst Compounds

Catalyst systems of the present disclosure may be formed by combiningthe catalysts with activators, including supporting the catalyst systemsfor use in slurry or gas phase polymerization. The catalyst systems mayalso be added to or generated in solution polymerization or bulkpolymerization (in the monomer, i.e., little or no solvent).

A transition metal compound capable of catalyzing a reaction, such as apolymerization reaction, upon activation with an activator as describedabove is suitable for use in polymerization reactor of the presentdisclosure. Transition metal compounds known as metallocenes areexemplary catalyst compounds according to the present disclosure.

In at least one embodiment, the present disclosure provides a catalystsystem including a catalyst compound having a metal atom. The catalystcompound can be a metallocene catalyst compound. The metal can be aGroup 3 through Group 12 metal atom, such as Group 3 through Group 10metal atoms, or lanthanide Group atoms. The catalyst compound having aGroup 3 through Group 12 metal atom can be monodentate or multidentate,such as bidentate, tridentate, or tetradentate, where a heteroatom ofthe catalyst, such as phosphorous, oxygen, nitrogen, or sulfur ischelated to the metal atom of the catalyst. Non-limiting examplesinclude bis(phenolate)s. In at least one embodiment, the Group 3 throughGroup 12 metal atom is selected from Group 5, Group 6, Group 8, or Group10 metal atoms. In at least one embodiment, a Group 3 through Group 10metal atom is selected from Cr, Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe,Ru, Os, Co, Rh, Ir, and Ni. In at least one embodiment, a metal atom isselected from Groups 4, 5, and 6 metal atoms. In at least oneembodiment, a metal atom is a Group 4 metal atom selected from Ti, Zr,or Hf. The oxidation state of the metal atom can be from 0 to +7, forexample +1, +2, +3, +4, or +5, such as +2, +3, or +4.

Metallocene Catalyst Compounds

A “metallocene” catalyst compound is a transition metal catalystcompound having one, two or three, typically one or two, substituted orunsubstituted cyclopentadienyl ligands (such as substituted orunsubstituted Cp, Ind or Flu) bound to the transition metal. Metallocenecatalyst compounds include metallocenes including Group 3 to Group 12metal complexes, such as, Group 4 to Group 6 metal complexes, forexample, Group 4 metal complexes. The metallocene catalyst compound ofcatalyst systems of the present disclosure may be unbridged metallocenecatalyst compounds represented by the formula: Cp^(A)Cp^(B)M′X′_(n),where each Cp^(A) and Cp^(B) is independently selected fromcyclopentadienyl ligands (for example, Cp, Ind, or Flu) and ligandsisolobal to cyclopentadienyl, one or both Cp^(A) and Cp^(B) may containheteroatoms, and one or both Cp^(A) and Cp^(B) may be substituted by oneor more R″ groups; M′ is selected from Groups 3 through 12 atoms andlanthanide Group atoms; X′ is an anionic leaving group; n is 0 or aninteger from 1 to 4; each R″ is independently selected from alkyl,substituted alkyl, heteroalkyl, alkenyl, substituted alkenyl,heteroalkenyl, alkynyl, substituted alkynyl, heteroalkynyl, alkoxy,aryloxy, alkylthio, arylthio, aryl, substituted aryl, heteroaryl,aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl,haloalkynyl, heteroalkyl, heterocycle, heteroaryl, aheteroatom-containing group, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine,ether, and thioether.

In at least one embodiment, each Cp^(A) and Cp^(B) is independentlyselected from cyclopentadienyl, indenyl, fluorenyl, indacenyl,tetrahydroindenyl, cyclopentaphenanthreneyl, benzindenyl, fluorenyl,octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene,phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl,8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl,indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl,hydrogenated and substituted versions thereof. Each Cp^(A) and Cp^(B)may independently be indacenyl or tetrahydroindenyl.

The metallocene catalyst compound may be a bridged metallocene catalystcompound represented by the formula: Cp^(A)(T)Cp^(B)M′X′_(n), where eachCp^(A) and Cp^(B) is independently selected from cyclopentadienylligands (for example, Cp, Ind, or Flu) and ligands isolobal tocyclopentadienyl, where one or both Cp^(A) and Cp^(B) may containheteroatoms, and one or both Cp^(A) and Cp^(B) may be substituted by oneor more R″ groups; M′ is selected from Groups 3 through 12 atoms andlanthanide Group atoms, such as Group 4; X′ is an anionic leaving group;n is 0 or an integer from 1 to 4; (T) is a bridging group selected fromdivalent alkyl, divalent substituted alkyl, divalent heteroalkyl,divalent alkenyl, divalent substituted alkenyl, divalent heteroalkenyl,divalent alkynyl, divalent substituted alkynyl, divalent heteroalkynyl,divalent alkoxy, divalent aryloxy, divalent alkylthio, divalentarylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl,divalent aralkyl, divalent aralkylene, divalent alkaryl, divalentalkarylene, divalent haloalkyl, divalent haloalkenyl, divalenthaloalkynyl, divalent heteroalkyl, divalent heterocycle, divalentheteroaryl, a divalent heteroatom-containing group, divalenthydrocarbyl, divalent substituted hydrocarbyl, divalentheterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphino,divalent phosphine, divalent amino, divalent amine, divalent ether,divalent thioether. R″ is selected from alkyl, substituted alkyl,heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl,substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio,arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene,alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl,heterocycle, heteroaryl, a heteroatom-containing group, hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino,phosphine, amino, amine, germanium, ether, and thioether.

In at least one embodiment, each of Cp^(A) and Cp^(B) is independentlyselected from cyclopentadienyl, indenyl, fluorenyl,cyclopentaphenanthreneyl, benzindenyl, fluorenyl, octahydrofluorenyl,cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl,3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl,7-H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl,thiophenofluorenyl, hydrogenated, and substituted versions thereof, suchas cyclopentadienyl, n-propylcyclopentadienyl, indenyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, andn-butylcyclopentadienyl. Each Cp^(A) and Cp^(B) may independently beindacenyl or tetrahydroindenyl.

(T) is a bridging group containing at least one Group 13, 14, 15, or 16element, in particular boron or a Group 14, 15 or 16 element, such aswhere (T) is 0, S, NR′, or SiR′₂, where each R′ is independentlyhydrogen or C₁-C₂ hydrocarbyl.

In another embodiment, the metallocene catalyst compound is representedby the formula:

T_(y)Cp_(m)MG_(n)X_(q)

where Cp is independently a substituted or unsubstitutedcyclopentadienyl ligand (for example, substituted or unsubstituted Cp,Ind, or Flu) or substituted or unsubstituted ligand isolobal tocyclopentadienyl; M is a Group 4 transition metal; G is a heteroatomgroup represented by the formula JR*_(z) where J is N, P, O or S, and R*is a linear, branched, or cyclic C₁-C₂₀ hydrocarbyl; z is 1 or 2; T is abridging group; y is 0 or 1; X is a leaving group; m=1, n=1, 2 or 3,q=0, 1, 2 or 3, and the sum of m+n+q is equal to the coordination numberof the transition metal.

In at least one embodiment, J is N, and R* is methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl,decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

In at least one embodiment, the catalyst compound is represented byformula (II) or formula (III):

where in each of formula (II) and formula (III):M is the metal center, and is a Group 4 metal, such as titanium,zirconium or hafnium, such as zirconium or hafnium when L₁ and L₂ arepresent and titanium when Z is present;n is 0 or 1;T is an optional bridging group which, if present, is a bridging groupcontaining at least one Group 13, 14, 15, or 16 element, in particularboron or a Group 14, 15 or 16 element (such as where T is selected fromdialkylsilyl, diaryIsilyl, dialkylnethyl, ethylenyl (—CH₂—CH₂—) orhydrocarbylethylenyl where one, two, three or four of the hydrogen atomsin ethylenyl are substituted by hydrocarbyl, where hydrocarbyl can beindependently C₁ to C₁₆ alkyl or phenyl, tolyl, xylyl and the like), andwhen T is present, the catalyst represented can be in a racemic or ameso form;L₁ and L₂ are independently cyclopentadienyl, indenyl, tetrahydroindenylor fluorenyl, optionally substituted, that are each bonded to M, or L₁and L₂ are independently cyclopentadienyl, indenyl, tetrahydroindenyl orfluorenyl, which are optionally substituted, in which two adjacentsubstituents on L¹ and L² are optionally joined to form a substituted orunsubstituted, saturated, partially unsaturated, or aromatic cyclic orpolycyclic substituent;Z is nitrogen, oxygen, sulfur, or phosphorus (such as nitrogen):q is 1 or 2 (such as where q is 1 when Z is N);R′ is a cyclic, linear or branched C₁ to C₄ alkyl or substituted alkylgroup;X₁ and X₂ are, independently, hydrogen, halogen, hydride radicals,hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbylradicals, substituted halocarbyl radicals, silylcarbyl radicals,substituted silylcarbyl radicals, germylcarbyl radicals, or substitutedgernylcarbyl radicals; or X₁ and X₂ are joined and bound to the metalatom to form a metallacycle ring containing from about 3 to about 20carbon atoms; or both together can be an olefin, diolefin or aryneligand.

In some embodiments, T is present and is a bridging group containing atleast one element from Group 13, 14, 15, or 16 of the periodic table ofthe elements, in particular a Group 14 element. Examples of suitablebridging groups include P(═S)R′, P(═Se)R′, P(═O)R′, R′₂C, R′₂Si, R′₂Ge,R′₂CCR′₂, R′₂CCR′₂CR′₂, R′₂CCR′₂CR′₂CR′₂, R′C═CR′, R′C═CR′CR′₂,R′₂CCR′═CR′CR′2, R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂, R′₂CSiR′₂, R′₂SiSiR′₂,R′₂SiOSiR′₂, R′₂CSiR′₂CR′₂, R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂, R′₂CGeR′₂,R′₂GeGeR′₂, R′₂CGeR′₂CR′₂, R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂, R′C═CR′GeR′₂,R′B, R′₂C—BR′, R′₂C—BR′—CR′₂, R′₂C—O—CR′₂, R′₂CR′₂C—O—CR′₂CR′₂,R′₂C—O—CR′₂CR′₂, R′₂C—O—CR′═CR′, R′₂C—S—CR′₂, R′₂CR′₂C—S—CR′₂CR′₂,R′₂C—S—CR′₂CR′₂, R′₂C—S—CR′═CR′, R′₂C—Se—CR′₂, R′₂CR′₂C—Se—CR′₂CR′₂,R′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′═CR′, R′₂C—N═CR′, R′₂C—NR′—CR′₂,R′₂C—NR′—CR′₂CR′₂, R′₂C—NR′—CR′═CR′, R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′,R′₂C—PR′—CR′₂, O, S, Se, Te, NR′, PR′, AsR′, SbR′, O—O, S—S, R′N—NR′,R′P—PR′, O—S, O—NR′, O—PR′, S—NR′, S—PR′, and R′N—PR′ where R′ ishydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbylsubstituent and optionally two or more adjacent R′ may join to form asubstituted or unsubstituted, saturated, partially unsaturated oraromatic, cyclic or polycyclic substituent. Examples for the bridginggroup T include CH₂, CH₂CH₂, SiMe₂, SiPh₂, SiMePh, Si(CH₂)₃, Si(CH₂)₄,O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me₂SiOSiMe₂, and PBu.

In some embodiments of formulas of the present disclosure, T isrepresented by the formula R^(a) ₂J or (R^(a) ₂J)₂, where J is C, Si, orGe, and each R^(a) is, independently, hydrogen, halogen, C₁ to C₂₀hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C₁ to C₂₀substituted hydrocarbyl, and two R^(a) can form a cyclic structureincluding aromatic, partially saturated, or saturated cyclic or fusedring system. In some embodiments, T is a bridging group including carbonor silica, such as dialkylsilyl, such as where T is selected from CH₂,CH₂CH₂, C(CH₃)₂, SiMe₂, SiPh₂, SiMePh, silylcyclobutyl (Si(CH₂)₃),(Ph)₂C, (p-(Et)₃SiPh)₂C, Me₂SiOSiMe₂, and cyclopentasilylene (Si(CH₂)₄).

In at least one embodiment, the catalyst compound has a symmetry that isC2 symmetrical.

The metallocene catalyst component may include a combination of two ormore “embodiments” of the present disclosure.

Suitable metallocenes include, but are not limited to, the metallocenesdisclosed and referenced in the US patents cited above, as well as thosedisclosed and referenced in U.S. Pat. Nos. 7,179,876; 7,169,864;7,157,531; 7,129,302; 6,995,109; 6,958,306; 6,884,748; 6,689,847; USPatent publication 2007/0055028, and published PCT Applications WO97/22635; WO 00/699/22; WO 01/30860; WO 01/30861; WO 02/46246; WO02/50088; WO 04/026921; and WO 06/019494, all incorporated by reference.Additional suitable catalysts include those referenced in U.S. Pat. Nos.6,309,997; 6,265,338; US Patent publication 2006/019925, and thefollowing articles: Resconi, L. et al. (2000) “Selectivity in PropenePolymerization with Metallocene Catalysts,” Chem. Rev., v. 100(4), pp.1253-1346; Gibson, V. C. et al. (2003) “Advances in Non-MetalloceneOlefin Polymerization Catalysis,” Chem. Rev., v. 103(1), pp. 283-316;Nakayama, Y. et al. (2006) “MgCl₂/R′_(n)Al(OR)_(3-n): An ExcellentActivator/Support for Transition-Metal Complexes for OlefinPolymerization,” Chem. Eur. J., v. 12, pp. 7546-7556; Nakayama, Y et al.(2004), “Olefin Polymerization Behavior of bis(phenoxy-imine) Zr, Ti,and V complexes with MgCl₂-based Cocatalysts,” J. Mol. Catalysis A:Chemical, v. 213, pp. 141-150; Nakayama, Y. et al. (2005), PropylenePolymerization Behavior of Fluorinated Bis(phenoxy-imine) Ti Complexeswith an MgCl₂—Based Compound (MgCl₂—Supported Ti-Based Catalysts),”Macromol. Chem. Phys., v. 206(18), pp. 1847-1852; and Matsui, S. et al.(2001) “A Family of Zirconium Complexes Having Two Phenoxy-Imine ChelateLigands for Olefin Polymerization,” J. Am. Chem. Soc., v. 123(28), pp.6847-6856.

Exemplary metallocene compounds include:

-   bis(cyclopentadienyl)zirconium dichloride,-   bis(n-butylcyclopentadienyl)zirconium dichloride,-   bis(n-butylcyclopentadienyl)zirconium dimethyl,-   bis(pentamethylcyclopentadienyl)zirconium dichloride,-   bis(pentamethylcyclopentadienyl)zirconium dimethyl,-   bis(pentamethylcyclopentadienyl)hafnium dichloride,-   bis(pentamethylcyclopentadienyl)zirconium dimethyl,-   bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride,-   bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,-   bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride,-   bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,-   bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl,-   bis(tetrahydro-1-indenyl)zirconium dichloride,-   bis(tetrahydro-1-indenyl)zirconium dimethyl,-   (n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium    dichloride, and-   (n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium    dimethyl.

In at least one embodiment, the catalyst compound may be selected from:

-   dimethylsilylbis(tetrahydroindenyl)MX_(n),-   dimethylsilylbis(2-methylindenyl)MX_(n),-   dimethylsilylbis(2-methylfluorenyl)MX_(n),-   dimethylsilylbis(2-methyl-5,7-propylindenyl)MX_(n),-   dimethylsilylbis(2-methyl-4-phenylindenyl)MX_(n),-   dimethylsilylbis(2-ethyl-5-phenylindenyl)MX_(n),-   dimethylsilylbis(2-methyl-4-biphenylindenyl)MX_(n),-   dimethylsilylenebis(2-methyl-4-carbazolylindenyl)MX_(n),-   rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)MX_(n),-   diphenylmethylene (cyclopentadienyl)(fluorenyl)MX_(n),-   bis(methylcyclopentadienyl)MX_(n),-   rac-dimethylsilylbis(2-methyl,3-propyl indenyl)MX_(n),-   dimethylsilylbis(indenyl)MX_(n),-   Rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)MX_(n),-   1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-1-fluorenyl)MX_(n)    (bridge is considered the 1 position),-   bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-t-butylfluorenyl)MXn,-   bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)MXn,-   bisphenylmethylene(cyclopentadienyl)(dimethylfluorenyl)MXn,-   bis(n-propylcyclopentadienyl)MX_(n),-   bis(n-butylcyclopentadienyl)MX_(n),-   bis(n-pentylcyclopentadienyl)MX_(n),-   (n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)MX_(n),-   bis[(2-trimethylsilylethyl)cyclopentadienyl]MX_(n),-   bis(trimethylsilyl cyclopentadienyl)MX_(n),-   dimethylsilylbis(n-propylcyclopentadienyl)MX_(n),-   dimethylsilylbis(n-butylcyclopentadienyl)MX_(n),-   bis(1-n-propyl-2-methylcyclopentadienyl)MX_(n),-   (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)MX_(n),-   bis(1-methyl, 3-n-butyl cyclopentadienyl)MX_(n),-   bis(indenyl)MX_(n),-   dimethylsilyl    (tetramethylcyclopentadienyl)(cyclododecylamido)MX_(n),-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)MX_(n),-   μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)MX_(n),-   μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)MX_(n),-   μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)MX_(n),-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)MX_(n),-   μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)MX_(n),-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)MX_(n),-   μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)MX_(n),-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)MX_(n),-   μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)MX_(n),-   μ-(CH₃)₂Si(η⁵-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)MX_(n),    where M is selected from Ti, Zr, and Hf; where X is selected from    the group consisting of halogens, hydrides, C₁₋₁₂ alkyls, C₂₋₁₂    alkenyls, C₆₋₁₂ aryls, C₇₋₂₀ alkylaryls, C₁₋₁₂ alkoxys, C₆₋₁₆    aryloxys, C₇₋₁₈ alkylaryloxys, C₁₋₁₂ fluoroalkyls, C₆₋₁₂    fluoroaryls, and C₁₋₁₂ heteroatom-containing hydrocarbons,    substituted derivatives thereof, and combinations thereof, and where    n is zero or an integer from 1 to 4, such as where X is selected    from halogens (such as bromide, fluoride, chloride), or C₁ to C₂₀    alkyls (such as methyl, ethyl, propyl, butyl, and pentyl) and n is 1    or 2.

In other embodiments, the catalyst is one or more of:

-   bis(1-methyl, 3-n-butyl cyclopentadienyl) M(R)₂;-   dimethylsilyl bis(indenyl)M(R)₂;-   bis(indenyl)M(R)₂;-   dimethylsilyl bis(tetrahydroindenyl)M(R)₂;-   bis(n-propylcyclopentadienyl)M(R)₂;-   dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)₂;-   dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)₂;-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)₂;    dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)₂;-   μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)M(R)₂;-   μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)₂;-   μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;-   μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)₂;-   μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M(R)₂;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;-   μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;-   μ-(CH₃)₂Si(η⁵-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)M(R)₂;    where M is selected from Ti, Zr, and Hf; and R is selected from    halogen or C₁ to C₅ alkyl.

In at least one embodiment, the catalyst compound is one or more of:

-   dimethylsilyl    (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl;-   dimethylsilyl    (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl;-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium    dimethyl;-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium    dimethyl;-   μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)titanium dimethyl;-   μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)titanium    dimethyl;-   μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)titanium    dimethyl;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)titanium    dimethyl;-   μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)titanium    dimethyl;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)titanium    dimethyl₂;-   μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)titanium dimethyl;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)titanium    dimethyl;-   μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)titanium    dimethyl; and/or-   μ-(CH₃)₂Si(η⁵-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)titanium    dimethyl.

In at least one embodiment, the catalyst israc-dimethylsilyl-bis(indenyl)hafnium dimethyl and or1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-1-fluorenyl)hafniumdimethyl.

In at least one embodiment, the catalyst compound is one or more of:

-   bis(1-methyl, 3-n-butyl cyclopentadienyl)hafnium dimethyl,-   bis(1-methyl, 3-n-butyl cyclopentadienyl)zirconium dimethyl,-   dimethylsilyl bis(indenyl)zirconium dimethyl,-   dimethylsilyl bis(indenyl)hafnium dimethyl,-   bis(indenyl)zirconium dimethyl,-   bis(indenyl)hafnium dimethyl,-   dimethylsilyl bis(tetrahydroindenyl)zirconium dimethyl,-   bis(n-propylcyclopentadienyl)zirconium dimethyl,-   dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl,-   dimethylsilyl bis(2-methylindenyl)zirconium dimethyl,-   dimethylsilyl bis(2-methylfluorenyl)zirconium dimethyl,-   dimethylsilyl bis(2-methylindenyl)hafnium dimethyl,-   dimethylsilyl bis(2-methylfluorenyl)hafnium dimethyl,-   dimethylsilyl bis(2-methyl-5,7-propylindenyl) zirconium dimethyl,-   dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl,-   dimethylsilyl bis(2-ethyl-5-phenylindenyl) zirconium dimethyl,-   dimethylsilyl bis(2-methyl-4-biphenylindenyl) zirconium dimethyl,-   dimethylsilylenebis(2-methyl-4-carbazolylindenyl) zirconium    dimethyl,-   rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)hafnium    dimethyl,-   diphenylmethylene (cyclopentadienyl)(fluorenyl)hafnium dimethyl,-   bis(methylcyclopentadienyl)zirconium dimethyl,-   rac-dimethylsilylbis(2-methyl,3-propyl indenyl)hafnium dimethyl,-   dimethylsilylbis(indenyl)hafnium dimethyl,-   dimethylsilylbis(indenyl)zirconium dimethyl,-   dimethyl    rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)hafnium    dimethyl,-   Rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)hafnium    dimethyl,-   1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-1-fluorenyl)hafnium    X_(n)(bridge is considered the 1 position),-   bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-t-butylfluorenyl)hafnium    dimethyl,-   bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)hafnium    dimethyl,-   bisphenylmethylene(cyclopentadienyl)(dimethylfluorenyl)hafnium    dimethyl,-   bis(n-propylcyclopentadienyl)hafnium dimethyl,-   bis(n-butylcyclopentadienyl)hafnium dimethyl,-   bis(n-pentylcyclopentadienyl)hafnium dimethyl,-   (n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)hafnium    dimethyl,-   bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl,-   bis(trimethylsilyl cyclopentadienyl)hafnium dimethyl,-   dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl,-   dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl,-   bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl, and-   (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium    dimethyl,-   bis(n-propylcyclopentadienyl)hafnium dimethyl,-   bis(n-butylcyclopentadienyl)hafnium dimethyl,-   bis(n-pentylcyclopentadienyl)hafnium dimethyl,-   (n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)hafnium    dimethyl,-   bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl,-   bis(trimethylsilyl cyclopentadienyl)hafnium dimethyl,-   dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl,-   dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl,-   bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl,-   (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium    dimethyl, and-   dimethylsilyl(3-n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium    dimethyl.

Non-Metallocene Catalyst Compounds

Transition metal complexes for polymerization processes can include anolefin polymerization catalyst. Suitable catalyst components may include“non-metallocene complexes” that are defined to be transition metalcomplexes that do not feature a cyclopentadienyl anion or substitutedcyclopentadienyl anion donors (e.g., cyclopentadienyl, fluorenyl,indenyl, methylcyclopentadienyl). Examples of families ofnon-metallocene complexes that may be suitable can include latetransition metal pyridylbisimines (e.g., U.S. Pat. No. 7,087,686), group4 pyridyldiamidos (e.g., U.S. Pat. No. 7,973,116), quinolinyldiamidos(e.g., U.S. Pub. No. 2018/0002352 A1), pyridylamidos (e.g., U.S. Pat.No. 7,087,690), phenoxyimines (e.g., Accounts of Chemical Research 2009,42, 1532-1544), and bridged bi-aromatic complexes (e.g., U.S. Pat. No.7,091,292), the disclosures of which are incorporated by reference.

Catalyst complexes that are suitable for use in combination with theactivators include: pyridyldiamido complexes; quinolinyldiamidocomplexes; phenoxyimine complexes; bisphenolate complexes;cyclopentadienyl-amidinate complexes; and iron pyridyl bis(imine)complexes or combinations thereof, including any suitable combinationwith metallocene complexes.

The term “pyridyldiamido complex” or “pyridyldiamide complex” or“pyridyldiamido catalyst” or “pyridyldiamide catalyst” refers to a classof coordination complexes described in U.S. Pat. No. 7,973,116B2, US2012/0071616A1, US 2011/0224391A1, US 2011/0301310A1, US 2015/0141601A1,U.S. Pat. Nos. 6,900,321 and 8,592,615 that feature a dianionictridentate ligand that is coordinated to a metal center through oneneutral Lewis basic donor atom (e.g., a pyridine group) and a pair ofanionic amido or phosphido (i.e., deprotonated amine or phosphine)donors. In these complexes the pyridyldiamido ligand is coordinated tothe metal with the formation of one five membered chelate ring and oneseven membered chelate ring. It is possible for additional atoms of thepyridyldiamido ligand to be coordinated to the metal without affectingthe catalyst function upon activation; an example of such coordinationcould be a cyclometalated substituted aryl group that forms anadditional bond to the metal center.

The term “quinolinyldiamido complex” or “quinolinyldiamido catalyst” or“quinolinyldiamide complex” or “quinolinyldiamide catalyst” refers to arelated class of pyridyldiamido complex/catalyst described in US2018/0002352 where a quinolinyl moiety is present instead of a pyridylmoiety.

The term “phenoxyimine complex” or “phenoxyimine catalyst” refers to aclass of coordination complexes described in EP 0 874 005 that feature amonoanionic bidentate ligand that is coordinated to a metal centerthrough one neutral Lewis basic donor atom (e.g., an imine moiety) andan anionic aryloxy (i.e., deprotonated phenoxy) donor. Typically two ofthese bidentate phenoxyimine ligands are coordinated to a group 4 metalto form a complex that is useful as a catalyst component.

The term “bisphenolate complex” or “bisphenolate catalyst” refers to aclass of coordination complexes described in U.S. Pat. No. 6,841,502, WO2017/004462, and WO 2006/020624 that feature a dianionic tetradentateligand that is coordinated to a metal center through two neutral Lewisbasic donor atoms (e.g., oxygen bridge moieties) and two anionic aryloxy(i.e., deprotonated phenoxy) donors.

The term “cyclopentadienyl-amidinate complex” or“cyclopentadienyl-amidinate catalyst” refers to a class of coordinationcomplexes described in U.S. Pat. No. 8,188,200 that typically feature agroup 4 metal bound to a cyclopentadienyl anion, a bidentate amidinateanion, and a couple of other anionic groups.

The term “iron pyridyl bis(imine) complex” refers to a class of ironcoordination complexes described in U.S. Pat. No. 7,087,686 thattypically feature an iron metal center coordinated to a neutral,tridentate pyridyl bis(imine) ligand and two other anionic ligands.

Non-metallocene complexes can include iron complexes of tridentatepyridylbisimine ligands, zirconium and hafnium complexes of pyridylamidoligands, zirconium and hafnium complexes of tridentate pyridyldiamidoligands, zirconium and hafnium complexes of tridentate quinolinyldiamidoligands, zirconium and hafnium complexes of bidentate phenoxyimineligands, and zirconium and hafnium complexes of bridged bi-aromaticligands.

Suitable non-metallocene complexes can include zirconium and hafniumnon-metallocene complexes. In at least one embodiment, non-metallocenecomplexes for the present disclosure include group 4 non-metallocenecomplexes including two anionic donor atoms and one or two neutral donoratoms. Suitable non-metallocene complexes for the present disclosureinclude group 4 non-metallocene complexes including an anionic amidodonor. Suitable non-metallocene complexes for the present disclosureinclude group 4 non-metallocene complexes including an anionic aryloxidedonor atom. Suitable non-metallocene complexes for the presentdisclosure include group 4 non-metallocene complexes including twoanionic aryloxide donor atoms and two additional neutral donor atoms.

A catalyst compounds can be a quinolinyldiamido (QDA) transition metalcomplex represented by Formula (BI), such as by Formula (BII), such asby Formula (BIII):

where:M is a group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal, such as a group 4metal;J is group including a three-atom-length bridge between the quinolineand the amido nitrogen, such as a group containing up to 50 non-hydrogenatoms;E is carbon, silicon, or germanium;X is an anionic leaving group, (such as a hydrocarbyl group or ahalogen);L is a neutral Lewis base;R¹ and R¹³ are independently selected from the group including ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², and R¹⁴are independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy,substituted hydrocarbyl, halogen, or phosphino;n is 1 or 2;m is 0, 1, or 2, wheren+m is not greater than 4; andtwo R groups (e.g., R¹ & R², R² & R³, R¹⁰ and R¹¹, etc.) may be joinedto form a substituted hydrocarbyl, unsubstituted hydrocarbyl,substituted heterocyclic, or unsubstituted heterocyclic, saturated orunsaturated ring, where the ring has 5, 6, 7, or 8 ring atoms and wheresubstitutions on the ring can join to form additional rings;two X groups may be joined together to form a dianionic group;two L groups may be joined together to form a bidentate Lewis base; andan X group may be joined to an L group to form a monoanionic bidentategroup.

In at least one embodiment, M is a group 4 metal, such as zirconium orhafnium, such as M is hafnium.

Representative non-metallocene transition metal compounds usable forforming poly(alpha-olefin)s of the present disclosure also includetetrabenzyl zirconium, tetra bis(trimethylsilymethyl) zirconium,oxotris(trimethlsilylmethyl) vanadium, tetrabenzyl hafnium, tetrabenzyltitanium, bis(hexamethyl disilazido)dimethyl titanium, tris(trimethylsilyl methyl) niobium dichloride, and tris(trimethylsilylmethyl)tantalum dichloride.

In at least one embodiment, J is an aromatic substituted orunsubstituted hydrocarbyl having from 3 to 30 non-hydrogen atoms, suchas J is represented by the formula:

such as J is

where R⁷, R⁸, R⁹, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², R¹⁴ and E are asdefined above, and two R groups (e.g., R⁷ & R⁸, R⁸ & R⁹, R⁹ & R¹⁰, R¹⁰ &R¹¹, etc.) may be joined to form a substituted or unsubstitutedhydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ringatoms (such as 5 or 6 atoms), and said ring may be saturated orunsaturated (such as partially unsaturated or aromatic), such as J is anarylalkyl (such as arylmethyl, etc.) or dihydro-1H-indenyl, ortetrahydronaphthalenyl group.

In at least one embodiment, J is selected from the following structures:

where

indicates connection to the complex.

In at least one embodiment, E is carbon.

X may be an alkyl (such as alkyl groups having 1 to 10 carbons, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, and isomers thereof), aryl, hydride, alkylsilane, fluoride,chloride, bromide, iodide, triflate, carboxylate, amido (such as NMe₂),or alkylsulfonate.

In at least one embodiment, L is an ether, amine or thioether.

In at least one embodiment, R⁷ and R⁸ are joined to form a six-memberedaromatic ring with the joined R⁷/R⁸ group being —CH═CHCH═CH—.

R¹⁰ and R¹¹ may be joined to form a five-membered ring with the joinedR¹⁰R¹¹ group being —CH₂CH₂—.

In at least one embodiment, R¹⁰ and R¹¹ are joined to form asix-membered ring with the joined R¹⁰R¹¹ group being —CH₂CH₂CH₂—.

R¹ and R¹³ may be independently selected from phenyl groups that arevariously substituted with zero to five substituents that include F, Cl,Br, I, CF₃, NO₂, alkoxy, dialkylamino, aryl, and alkyl groups having 1to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, and isomers thereof.

In at least one embodiment, the QDA transition metal complex representedby the Formula (II) above where:

M is a group 4 metal (such hafnium);E is selected from carbon, silicon, or germanium (such as carbon);X is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide,iodide, triflate, carboxylate, amido, alkoxo, or alkylsulfonate;L is an ether, amine, or thioether;R¹ and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups (such as aryl);R², R³, R⁴, R⁶, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independentlyhydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substitutedhydrocarbyls, halogen, and phosphino;n is 1 or 2;m is 0, 1, or 2;n+m is from 1 to 4;two X groups may be joined together to form a dianionic group;two L groups may be joined together to form a bidentate Lewis base;an X group may be joined to an L group to form a monoanionic bidentategroup;R⁷ and R⁸ may be joined to form a ring (such as an aromatic ring, asix-membered aromatic ring with the joined R⁷R⁸ group being—CH═CHCH═CH—); andR¹⁰ and R¹¹ may be joined to form a ring (such as a five-membered ringwith the joined R¹⁰R¹¹ group being —CH₂CH₂—, a six-membered ring withthe joined R¹⁰R¹¹ group being —CH₂CH₂CH₂—).

In at least one embodiment of Formula (BI), (BII), and (BIII), R⁴, R⁵,and R⁶ are independently selected from the group including hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino,and silyl, and where adjacent R groups (R⁴ and R⁵ and/or R⁵ and R⁶) arejoined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl,unsubstituted heterocyclic ring or substituted heterocyclic ring, wherethe ring has 5, 6, 7, or 8 ring atoms and where substitutions on thering can join to form additional rings.

In at least one embodiment of Formula (BI), (BII), and (BII), R⁷, R⁸,R⁹, and R¹⁰ are independently selected from the group includinghydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen,amino, and silyl, and where adjacent R groups (R⁷ and R⁸ and/or R⁹ andR¹⁰) may be joined to form a saturated, substituted hydrocarbyl,unsubstituted hydrocarbyl, unsubstituted heterocyclic ring orsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ringcarbon atoms and where substitutions on the ring can join to formadditional rings.

In at least one embodiment of Formula (BI), (BII), and (BIII), R² and R³are each, independently, selected from the group including hydrogen,hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino,aryloxy, halogen, and phosphino, R² and R³ may be joined to form asaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ringcan join to form additional rings, or R² and R³ may be joined to form asaturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings.

In at least one embodiment of Formula (BI), (BII), and (BIII), R¹¹ andR¹² are each, independently, selected from the group including hydrogen,hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino,aryloxy, halogen, and phosphino, R¹¹ and R¹² may be joined to form asaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ringcan join to form additional rings, or R¹¹ and R¹² may be joined to forma saturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings,or R¹¹ and R¹⁰ may be joined to form a saturated heterocyclic ring, or asaturated substituted heterocyclic ring where substitutions on the ringcan join to form additional rings.

In at least one embodiment of Formula (BI), (BII), and (BIII), R¹ andR¹³ are independently selected from phenyl groups that are variouslysubstituted with zero to five substituents that include F, Cl, Br, I,CF₃, NO₂, alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, and isomers thereof.

In at least one embodiment of Formula (BII), suitable R¹²-E-R¹¹ groupsinclude CH₂, CMe₂, SiMe₂, SiEt₂, SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂,Si(alkyl)₂, CH(aryl), CH(Ph), CH(alkyl), and CH(2-isopropylphenyl),where alkyl is a C₁ to C₄₀ alkyl group (such as C₁ to C₂₀ alkyl, such asone or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is aC₅ to C₄₀ aryl group (such as a C₆ to C₂₀ aryl group, such as phenyl orsubstituted phenyl, such as phenyl, 2-isopropylphenyl, or2-tertbutylphenyl).

In at least one embodiment of Formula (BIII), R¹¹, R¹², R⁹, R¹⁴, and R¹⁰are independently selected from the group consisting of hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, andsilyl, and where adjacent R groups (R¹⁰ and R¹⁴, and/or R¹¹ and R¹⁴,and/or R⁹ and R¹⁰) may be joined to forma saturated, substitutedhydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ringor substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ringcarbon atoms and where substitutions on the ring can join to formadditional rings.

The R groups above (such as, individually R² to R¹⁴) and other R groupsmentioned hereafter may contain from 1 to 30, such as 2 to 20 carbonatoms, such as from 6 to 20 carbon atoms. The R groups above (such as,individually R² to R¹⁴) and other R groups mentioned hereafter, may beindependently selected from the group including hydrogen, methyl, ethyl,phenyl, isopropyl, isobutyl, trimethylsilyl, and —CH₂—Si(Me)₃.

In at least one embodiment, the quinolinyldiamide complex is linked toone or more additional transition metal complex, such as aquinolinyldiamide complex or another suitable non-metallocene, throughan R group in such a fashion as to make a bimetallic, trimetallic, ormultimetallic complex that may be used as a catalyst component forolefin polymerization. The linker R-group in such a complex may contain1 to 30 carbon atoms.

In at least one embodiment, E is carbon and R and R¹² are independentlyselected from phenyl groups that are substituted with 0, 1, 2, 3, 4, or5 substituents selected from the group consisting of F, Cl, Br, I, CF₃,NO₂, alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbylgroups with from one to ten carbons.

In at least one embodiment of Formula (BI) or (BIII), R¹¹ and R¹² areindependently selected from hydrogen, methyl, ethyl, phenyl, isopropyl,isobutyl, —CH₂—Si(Me)₃, and trimethylsilyl.

In at least one embodiment of Formula (BIT), and (BIII), R⁷, R⁸, R⁹, andR¹⁰ are independently selected from hydrogen, methyl, ethyl, propyl,isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy,—CH₂—Si(Me)₃, and trimethylsilyl.

In at least one embodiment of Formula (BI), (BII), and (BIII), R², R³,R⁴, R⁵, and R⁶ are independently selected from the group consisting ofhydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls,and halogen.

In at least one embodiment of Formula (BIII), R¹⁰, R¹¹ and R¹⁴ areindependently selected from hydrogen, methyl, ethyl, phenyl, isopropyl,isobutyl, —CH₂—Si(Me)₃, and trimethylsilyl.

In at least one embodiment of Formula (BI), (BII), and (BIII), each L isindependently selected from Et₂O, MeOtBu, Et₃N, PhNMe₂, MePh₂N,tetrahydrofuran, and dimethylsulfide.

In at least one embodiment of Formula (BI), (BII), and (BIII), each X isindependently selected from methyl, benzyl, trimethylsilyl, neopentyl,ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo,dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

In at least one embodiment of Formula (BI), (BIT), and (BITT), R¹ is2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl,2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl,2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl,2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

In at least one embodiment of Formula (BI), (BII), and (BIT), R¹³ isphenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl,2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl,3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl,3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

In at least one embodiment of Formula (BII), J is dihydro-1H-indenyl andR¹ is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.

In at least one embodiment of Formula (BI), (BII), and (BIII), R¹ is2,6-diisopropylphenyl and R¹³ is a hydrocarbyl group containing 1, 2, 3,4, 5, 6, or 7 carbon atoms.

An exemplary catalyst used for polymerizations of the present disclosureis (QDA-1)HfMe₂, as described in U.S. Pub. No. 2018/0002352 A1.

In at least one embodiment, the catalyst compound is a bis(phenolate)catalyst compound represented by Formula (CI):

M is a Group 4 metal, such as Hf or Zr. X and X2 are independently aunivalent C₁-C₂₀ hydrocarbyl, C₁-C₂₀ substituted hydrocarbyl, aheteroatom or a heteroatom-containing group, or X¹ and X² join togetherto form a C₄-C₆₂ cyclic or polycyclic ring structure. R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently hydrogen, C₁-C₄₀hydrocarbyl, C₁-C₄ substituted hydrocarbyl, a heteroatom or aheteroatom-containing group, or two or more of R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, or R¹⁰ are joined together to form a C₄-C₆₂ cyclic orpolycyclic ring structure, or a combination thereof; Q is a neutraldonor group; J is heterocycle, a substituted or unsubstituted C₇-C₆₀fused polycyclic group, where at least one ring is aromatic and where atleast one ring, which may or may not be aromatic, has at least five ringatoms' G is as defined for J or may be hydrogen, C₂-C₆₀ hydrocarbyl,C₁-C₆₀ substituted hydrocarbyl, or may independently form a C₄-C₆₀cyclic or polycyclic ring structure with R⁶, R⁷, or R⁸ or a combinationthereof; Y is divalent C₁-C₂₀ hydrocarbyl or divalent C₁-C₂₀ substitutedhydrocarbyl or (-Q-Y—) together form a heterocycle; and heterocycle maybe aromatic and/or may have multiple fused rings.

In at least one embodiment, the catalyst compound represented by Formula(CI) is represented by Formula (CII) or Formula (CIII):

M is Hf, Zr, or Ti. X¹, X², R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, andY are as defined for Formula (CI). R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ isindependently a hydrogen, C₁-C₄₀ hydrocarbyl, C₁-C₄₀ substitutedhydrocarbyl, a functional group including elements from Groups 13 to 17,or two or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,R²⁷, and R²⁸ may independently join together to form a C₄-C₆₂ cyclic orpolycyclic ring structure, or a combination thereof; R and R¹² may jointogether to form a five- to eight-membered heterocycle; Q* is a group 15or 16 atom; z is 0 or 1; J* is CR″ or N, and G* is CR″ or N, where R″ isC₁-C₂₀ hydrocarbyl or carbonyl-containing C₁-C₂ hydrocarbyl; and z=0 ifQ* is a group 16 atom, and z=1 if Q* is a group 15 atom.

In at least one embodiment the catalyst is an iron complex representedby formula (IV):

where:A is chlorine, bromine, iodine, —CF₃ or —OR¹¹;each of R¹ and R² is independently hydrogen, C₁-C₂₂-alkyl,C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to 10carbon atoms and aryl has from 6 to 20 carbon atoms, or five-, six- orseven-membered heterocyclyl including at least one atom selected fromthe group consisting of N, P, O and S;where each of R and R² is optionally substituted by halogen, —NR¹¹ ₂,—OR¹¹ or —SiR¹² ₃; where R¹ optionally bonds with R³, and R² optionallybonds with R⁵, in each case to independently form a five-, six- orseven-membered ring;R⁷ is a C₁-C₂₀ alkyl;each of R³, R⁴, R⁵, R⁸, R⁹, R¹⁰, R¹⁵, R¹⁶, and R¹⁷ is independentlyhydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl wherealkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbonatoms, —NR¹¹ ₂, —OR¹¹, halogen, —SiR¹² ₃ or five-, six- orseven-membered heterocyclyl including at least one atom selected fromthe group consisting of N, P, O, and S; where R³, R⁴, R⁵, R⁷, R⁸, R⁹,R¹⁰, R¹⁵, R¹⁶, and R¹⁷ are optionally substituted by halogen, —NR¹¹ ₂,—OR¹¹ or —SiR¹² ₃;where R³ optionally bonds with R⁴, R⁴ optionally bonds with R⁵, R⁷optionally bonds with R¹⁰, R¹⁰ optionally bonds with R⁹, R⁹ optionallybonds with R⁸, R¹⁷ optionally bonds with R¹⁶, andR¹⁶ optionally bonds with R¹⁵, in each case to independently form afive-, six- or seven-membered carbocyclic or heterocyclic ring, theheterocyclic ring including at least one atom from the group consistingof N, P, O and S;R¹³ is C₁-C₂₀-alkyl bonded with the aryl ring via a primary or secondarycarbon atom;R¹⁴ is chlorine, bromine, iodine, —CF₃ or —OR¹¹, or C₁-C₂₀-alkyl bondedwith the aryl ring; each R¹¹ is independently hydrogen, C₁-C₂₂-alkyl,C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to 10carbon atoms and aryl has from 6 to 20 carbon atoms, or —SiR¹² ₃, whereR¹¹ is optionally substituted by halogen, or two R¹¹ radicals optionallybond to form a five- or six-membered ring;each R¹² is independently hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl,C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms andaryl has from 6 to 20 carbon atoms, or two R¹² radicals optionally bondto form a five- or six-membered ring;each of E¹, E², and E³ is independently carbon, nitrogen or phosphorus;each u is independently 0 if E¹, E², and E³ is nitrogen or phosphorusand is 1 if E¹, E², and E³ is carbon;each X is independently fluorine, chlorine, bromine, iodine, hydrogen,C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₆-C₂-aryl, arylalkyl where alkyl has from1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR¹⁸ ₂,—OR¹⁸, —SR¹⁸, —SO₃R¹⁸, —OC(O)R¹⁸, —CN, —SCN, β-diketonate, —CO, —BF₄—,—PF₆— or bulky non-coordinating anions, and the radicals X can be bondedwith one another;each R⁸ is independently hydrogen, C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₆-C₂₀-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms andaryl has from 6 to 20 carbon atoms, or —SiR¹⁹ ₃, where R¹⁸ can besubstituted by halogen or nitrogen- or oxygen-containing groups and twoR¹⁸ radicals optionally bond to form a five- or six-membered ring;each R¹⁹ is independently hydrogen, C₁-C₂-alkyl, C₂-C₂₀-alkenyl,C₆-C₂-aryl or arylalkyl where alkyl has from 1 to 10 carbon atoms andaryl has from 6 to 20 carbon atoms, where R¹⁹ can be substituted byhalogen or nitrogen- or oxygen-containing groups or two R¹⁹ radicalsoptionally bond to form a five- or six-membered ring;s is 1, 2, or 3;D is a neutral donor; andt is 0 to 2.

In another embodiment, the catalyst is a phenoxyimine compoundrepresented by the formula (VII):

where M represents a transition metal atom selected from the groups 3 to11 metals in the periodic table; k is an integer of 1 to 6; m is aninteger of 1 to 6; R^(a) to R^(f) may be the same or different from oneanother and each represent a hydrogen atom, a halogen atom, ahydrocarbon group, a heterocyclic compound residue, an oxygen-containinggroup, a nitrogen-containing group, a boron-containing group, asulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group, among which 2 or more groups may be bound to eachother to form a ring; when k is 2 or more, R^(a) groups, R^(b) groups,R^(c) groups, R^(d) groups, R^(e) groups, or R^(f) groups may be thesame or different from one another, one group of R^(a) to R^(f)contained in one ligand and one group of R^(a) to R^(f) contained inanother ligand may form a linking group or a single bond, and aheteroatom contained in R^(a) to R^(f) may coordinate with or bind to M;m is a number satisfying the valence of M; Q represents a hydrogen atom,a halogen atom, an oxygen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group; when m is 2 or more, a plurality of groupsrepresented by Q may be the same or different from one another, and aplurality of groups represented by Q may be mutually bound to form aring.

In another embodiment, the catalyst is a bis(imino)pyridyl of theformula (VIII):

where:M is Co or Fe; each X is an anion; n is 1, 2 or 3, so that the totalnumber of negative charges on said anion or anions is equal to theoxidation state of a Fe or Co atom present in (VIII);R¹, R² and R³ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or an inert functional group;R⁴ and R⁵ are each independently hydrogen, hydrocarbyl, an inertfunctional group or substituted hydrocarbyl;

R⁶ is formula IX:

and R⁷ is formula X:

R⁸ and R¹³ are each independently hydrocarbyl, substituted hydrocarbylor an inert functional group;R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁵ and R¹⁶ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or an inert functional group;R¹² and R¹⁷ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or an inert functional group;and provided that two of R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶ andR¹⁷ that are adjacent to one another, together may form a ring.

In at least one embodiment, the catalyst compound is represented by theformula (XI):

M¹ is selected from the group consisting of titanium, zirconium,hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten.In at least one embodiment, M¹ is zirconium.

Each of Q¹, Q², Q³, and Q⁴ is independently oxygen or sulfur. In atleast one embodiment, at least one of Q¹, Q², Q³, and Q⁴ is oxygen,alternately all of Q¹, Q², Q³, and Q⁴ are oxygen.

R¹ and R² are independently hydrogen, halogen, hydroxyl, hydrocarbyl, orsubstituted hydrocarbyl (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₂₀aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄ arylalkyl,C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, or conjugated diene which isoptionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl or tri(hydrocarbyl) silylhydrocarbyl, the diene having up to 30atoms other than hydrogen). R¹ and R² can be a halogen selected fromfluorine, chlorine, bromine, or iodine. In at least one embodiment, R¹and R² are chlorine.

Alternatively, R¹ and R² may also be joined together to form analkanediyl group or a conjugated C₄-C₄₀ diene ligand which iscoordinated to M. R¹ and R² may also be identical or differentconjugated dienes, optionally substituted with one or more hydrocarbyl,tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the dieneshaving up to 30 atoms not counting hydrogen and/or forming a π-complexwith M¹.

Exemplary groups suitable for R¹ and or R² can include 1,4-diphenyl,1,3-butadiene, 1,3-pentadiene, 2-methyl 1,3-pentadiene, 2,4-hexadiene,1-phenyl, 1,3-pentadiene, 1,4-dibenzyl, 1,3-butadiene,1,4-ditolyl-1,3-butadiene, 1,4-bis (trimethylsilyl)-1,3-butadiene, and1,4-dinaphthyl-1,3-butadiene. R and R² can be identical and are C₁-C₃alkyl or alkoxy, C₆-C₁₀ aryl or aryloxy, C₂-C₄ alkenyl, C₇-C₁₀arylalkyl, C₇-C₁₂ alkylaryl, or halogen.

Each of R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, and R¹⁹ is independently hydrogen, halogen, C₁-C₄₀ hydrocarbyl orC₁-C₄₀ substituted hydrocarbyl (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy,C₆-C₂₀ aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, or conjugated dienewhich is optionally substituted with one or more hydrocarbyl,tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the dienehaving up to 30 atoms other than hydrogen), —NR′₂, —SR′, —OR, —OSiR′₃,—PR′₂, where each R′ is hydrogen, halogen, C₁-C₁₀ alkyl, or C₆-C₁₀ aryl,or one or more of R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R⁸ and R⁹, R⁹ andR¹⁰, R¹⁰ and R¹¹, R¹² and R¹³, R¹³ and R¹⁴, R¹⁴ and R¹⁵, R¹⁶ and R¹⁷,R¹⁷ and R¹⁸, and R¹⁸ and R¹⁹ are joined to form a saturated ring,unsaturated ring, substituted saturated ring, or substituted unsaturatedring. In at least one embodiment, C₁-C₄₀ hydrocarbyl is selected frommethyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl,sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl,sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, andsec-decyl. In at least one embodiment, R¹¹ and R¹² are C₆-C₁₀ aryl suchas phenyl or naphthyl optionally substituted with C₁-C₄₀ hydrocarbyl,such as C₁-C₁₀ hydrocarbyl. In at least one embodiment, R⁶ and R¹⁷ areC₁₋₄₀ alkyl, such as C₁-C₁₀ alkyl.

In at least one embodiment, each of R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ is independently hydrogen or C₁-C₄₀hydrocarbyl. In at least one embodiment, C₁-C₄₀ hydrocarbyl is selectedfrom methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl,sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl,sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, andsec-decyl. In at least one embodiment, each of R⁶ and R¹ is C₁-C₄₀hydrocarbyl and R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁸, andR¹⁹ is hydrogen. In at least one embodiment, C₁-C₄₀ hydrocarbyl isselected from methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl,sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl,sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, andsec-decyl.

R³ is a C₁-C₄₀ unsaturated alkyl or substituted C₁-C₄₀ unsaturated alkyl(such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₂₀ aryl, C₆-C₁₀ aryloxy,C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl,C₈-C₄₀ arylalkenyl, or conjugated diene which is optionally substitutedwith one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl)silylhydrocarbyl, the diene having up to 30 atoms other than hydrogen).

In at least one embodiment, R³ is a hydrocarbyl including a vinylmoiety. The terms “vinyl” and “vinyl moiety” are used interchangeablyand include a terminal alkene, e.g., represented by the structure

Hydrocarbyl of R³ may be further substituted (such as C₁-C₁₀ alkyl,C₁-C₁₀ alkoxy, C₆-C₂ aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, orconjugated diene which is optionally substituted with one or morehydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl)silylhydrocarbyl, the diene having up to 30 atoms other than hydrogen).In at least one embodiment, R³ is C₁-C₄₀ unsaturated alkyl that is vinylor substituted C₁-C₄₀ unsaturated alkyl that is vinyl. R³ can berepresented by the structure —R′CH═CH₂ where R′ is C₁-C₄₀ hydrocarbyl orC₁-C₄₀ substituted hydrocarbyl (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy,C₆-C₂₀ aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, or conjugated dienewhich is optionally substituted with one or more hydrocarbyl,tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the dienehaving up to 30 atoms other than hydrogen). In at least one embodiment,C₁-C₄₀ hydrocarbyl is selected from methyl, ethyl, propyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl,sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl,sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl,n-decyl, isodecyl, and sec-decyl.

In at least one embodiment, R³ is 1-propenyl, 1-butenyl, 1-pentenyl,1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, or 1-decenyl.

In at least one embodiment, the catalyst is a Group 15-containing metalcompound represented by Formulas (XII) or (XIII):

where M is a Group 3 to 12 transition metal or a Group 13 or 14 maingroup metal, a Group 4, 5, or 6 metal. In some embodiments, M is a Group4 metal, such as zirconium, titanium, or hafnium. Each X isindependently a leaving group, such as an anionic leaving group. Theleaving group may include a hydrogen, a hydrocarbyl group, a heteroatom,a halogen, or an alkyl; y is 0 or 1 (when y is 0 group L′ is absent).The term “n” is the oxidation state of M. In various embodiments, n is+3, +4, or +5. In some embodiments, n is +4. The term “m” represents theformal charge of the YZL or the YZL′ ligand, and is 0, −1, −2 or −3 invarious embodiments. In some embodiments, m is −2. L is a Group 15 or 16element, such as nitrogen or oxygen; L′ is a Group 15 or 16 element orGroup 14 containing group, such as carbon, silicon or germanium. Y is aGroup 15 element, such as nitrogen or phosphorus. In some embodiments, Yis nitrogen. Z is a Group 15 element, such as nitrogen or phosphorus. Insome embodiments, Z is nitrogen. R¹ and R² are, independently, a C₂ toC₂₀ hydrocarbon group, a heteroatom containing group having up to twentycarbon atoms, silicon, germanium, tin, lead, or phosphorus. In someembodiments, R¹ and R² are a C₂ to C₂₀ alkyl, aryl or aralkyl group,such as a C₂ to C₂₀ linear, branched or cyclic alkyl group, or a C₂ toC₂₀ hydrocarbon group. R¹ and R² may also be interconnected to eachother. R³ may be absent or may be a hydrocarbon group, a hydrogen, ahalogen, a heteroatom containing group. In some embodiments, R³ isabsent, for example, if L is an oxygen, or a hydrogen, or a linear,cyclic, or branched alkyl group having 1 to 20 carbon atoms. R⁴ and R⁵are independently an alkyl group, an aryl group, substituted aryl group,a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkylgroup, a substituted cyclic aralkyl group, or multiple ring system,often having up to 20 carbon atoms. In some embodiments, R⁴ and R⁵ have3 to 10 carbon atoms, or are a C₁ to C₂₀ hydrocarbon group, a C₁ to C₂₀aryl group or a C₁ to C₂₀ aralkyl group, or a heteroatom containinggroup. R⁴ and R⁵ may be interconnected to each other. R⁶ and R⁷ areindependently absent, hydrogen, an alkyl group, halogen, heteroatom, ora hydrocarbyl group, such as a linear, cyclic or branched alkyl grouphaving 1 to 20 carbon atoms. In some embodiments, R⁶ and R⁷ are absent.R* may be absent, or may be a hydrogen, a Group 14 atom containinggroup, a halogen, or a heteroatom containing group.

The term “formal charge of the YZL or YZL′ ligand,” means the charge ofthe entire ligand absent the metal and the leaving groups X. By “R¹ andR² may also be interconnected” it is meant that R¹ and R² may bedirectly bound to each other or may be bound to each other through othergroups. By “R⁴ and R⁵ may also be interconnected” it is meant that R⁴and R⁵ may be directly bound to each other or may be bound to each otherthrough other groups. An alkyl group may be linear, branched alkylradicals, alkenyl radicals, alkynyl radicals, cycloalkyl radicals, arylradicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

In one or more embodiments, R⁴ and R⁵ are independently a grouprepresented by structure (XIV):

where R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a halide, a heteroatom, a heteroatom containing group containingup to 40 carbon atoms. In some embodiments, R to R¹² are a C₁ to C₂₀linear or branched alkyl group, such as a methyl, ethyl, propyl, orbutyl group. Two of the R groups may form a cyclic group and/or aheterocyclic group. The cyclic groups may be aromatic. In at least oneembodiment R⁹, R¹⁰ and R¹² are independently a methyl, ethyl, propyl, orbutyl group (including all isomers). In another embodiment, R⁹, R¹⁰ andR¹² are methyl groups, and R⁸ and R¹¹ are hydrogen.

In one or more embodiments, R⁴ and R⁵ are both a group represented bystructure (XV):

where M is a Group 4 metal, such as zirconium, titanium, or hafnium. Inat least one embodiment, M is zirconium. Each of L, Y, and Z may be anitrogen. Each of R¹ and R² may be —CH₂—CH₂—. R³ may be hydrogen, and R⁶and R⁷ may be absent.

In one or more embodiments, the catalyst compounds described inPCT/US2018/051345, filed Sep. 17, 2018 may be used with the activators,including the catalyst compounds described at Page 16 to Page 32 of theapplication as filed.

In some embodiments, a co-activator is combined with the catalystcompound (such as halogenated catalyst compounds described above) toform an alkylated catalyst compound. Organoaluminum compounds which maybe utilized as co-activators include, for example, trialkyl aluminumcompounds, such as trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and thelike, or alumoxanes.

In some embodiments, two or more different catalyst compounds arepresent in the catalyst system. In some embodiments, two or moredifferent catalyst compounds are present in the reaction zone where thepolymerization process(es) occur. When two transition metal compoundbased catalysts are used in one reactor as a mixed catalyst system, thetwo transition metal compounds may be chosen such that the two arecompatible. A simple screening method such as by ¹H or ¹³C NMR, can beused to determine which transition metal compounds are compatible. It ispreferable to use the same activator for the transition metal compounds,however, two different activators can be used in combination. If one ormore transition metal compounds contain an anionic ligand as a leavinggroup which is not a hydride, hydrocarbyl, or substituted hydrocarbyl,then the alumoxane or other alkyl aluminum is typically contacted withthe transition metal compounds prior to addition of the non-coordinatinganion activator.

The two transition metal compounds (pre-catalysts) may be used in anysuitable ratio. Molar ratios of (A) transition metal compound to (B)transition metal compound may (A:B) may be from 1:1000 to 1000:1, from1:100 to 500:1, from 1:10 to 200:1, from 1:1 to 100:1, from 1:1 to 75:1,or from 5:1 to 50:1. The particular ratio chosen will depend on theexact pre-catalysts chosen, the method of activation, and the endproduct. In a particular embodiment, when using the two pre-catalysts,where both are activated with the same activator, useful mole percent,based upon the molecular weight of the pre-catalysts, are 10 to 99.9 mol% A to 0.1 to 90 mol % B, 25 to 99 mol % A to 0.5 to 50 mol % B, 50 to99 mol % A to 1 to 25 mol % B, or 75 to 99 mol % A to 1 to 10 mol % B.

Support Materials

In some embodiments, the catalyst system may include a support material.In at least one embodiment, the support material is a porous supportmaterial, for example, talc, or inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other suitableorganic or inorganic support material and the like, or mixtures thereof.

In at least one embodiment, the support material is an inorganic oxide.Suitable inorganic oxide materials for use in catalyst systems includeGroups 2, 4, 13, and 14 metal oxides, such as silica, alumina, andmixtures thereof. Other inorganic oxides that may be employed eitheralone or in combination with the silica, or alumina are magnesia,titania, zirconia, and the like. Other suitable support materials,however, can be used, for example, functionalized polyolefins, such aspolypropylene. Supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania, and the like. Supportmaterials include Al₂O₃, ZrO₂, SiO₂, SiO₂/Al₂O₃, SiO₂/TiO₂, silica clay,silicon oxide/clay, or mixtures thereof.

The support material, such as an inorganic oxide, can have a surfacearea of from 10 m²/g to 700 m²/g, pore volume of from 0.1 cc/g to 4 cc/gand average particle size of from 5 μm to 500 μm. In at least oneembodiment, the surface area of the support material is of from 50 m²/gto 500 m²/g, pore volume of from 0.5 cc/g to 3.5 cc/g and averageparticle size of from 10 μm to 200 μm. In at least one embodiment, thesurface area of the support material is from 100 m²/g to 400 m²/g, porevolume from 0.8 cc/g to 3 cc/g and average particle size is from 5 μm to100 μm. The average pore size of the support material useful in thepresent disclosure is from 10 Å to 1000 Å, such as 50 Å to 500 Å, suchas 75 Å to 350 Å. In some embodiments, the support material is a highsurface area, amorphous silica (surface area=300 m²/gm; pore volume of1.65 cm³/gm). Exemplary silicas are marketed under the tradenames ofDAVISON 952 or DAVISON 955 by the Davison Chemical Division of W.R.Grace and Company. In other embodiments DAVISON 948 is used.

The support material should be dry, that is, substantially free ofabsorbed water. Drying of the support material can be effected byheating or calcining at 100° C. to 1000° C., such as at least about 600°C. When the support material is silica, the silica is heated to at least200° C., such as 200° C. to 850° C., such as at about 600° C.; and for atime of 1 minute to about 100 hours, from 12 hours to 72 hours, or from24 hours to 60 hours. The calcined support material should have at leastsome reactive hydroxyl (OH) groups to produce supported catalyst systemsof the present disclosure. The calcined support material is thencontacted with at least one polymerization catalyst including at leastone catalyst compound and an activator.

The support material, having reactive surface groups, typically hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a catalyst compound and an activator. Insome embodiments, the slurry of the support material is first contactedwith the activator from 0.5 hours to 24 hours, from 2 hours to 16 hours,or from 4 hours to 8 hours. The solution of the catalyst compound isthen contacted with the isolated support/activator. In some embodiments,the supported catalyst system is generated in situ. In at least oneembodiment, the slurry of the support material is first contacted withthe catalyst compound from 0.5 hours to 24 hours, from 2 hours to 16hours, or from 4 hours to 8 hours. The slurry of the supported catalystcompound is then contacted with the activator solution.

The mixture of the catalyst, activator and support is heated to 0° C. to70° C., such as to 23° C. to 60° C., such as at room temperature.Contact times are typically from 0.5 hours to 24 hours, from 2 hours to16 hours, or from 4 hours to 8 hours.

Suitable non-polar solvents are materials in which all of the reactants,e.g., the activator, and the catalyst compound, are at least partiallysoluble and which are liquid at room temperature. Non-limiting examplenon-polar solvents are alkanes, such as isopentane, hexane, n-heptane,octane, nonane, and decane, cycloalkanes, such as cyclohexane,aromatics, such as benzene, toluene, and ethylbenzene.

In at least one embodiment, the support material includes a supportmaterial treated with an electron-withdrawing anion. The supportmaterial can be silica, alumina, silica-alumina, silica-zirconia,alumina-zirconia, aluminum phosphate, heteropolytungstates, titania,magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof;and the electron-withdrawing anion is selected from fluoride, chloride,bromide, phosphate, triflate, bisulfate, sulfate, or combinationsthereof.

The electron-withdrawing component used to treat the support materialcan be any suitable component that increases the Lewis or Brønstedacidity of the support material upon treatment (as compared to thesupport material that is not treated with at least oneelectron-withdrawing anion). In at least one embodiment, theelectron-withdrawing component is an electron-withdrawing anion derivedfrom a salt, an acid, or other compound, such as a volatile organiccompound, that serves as a source or precursor for that anion.Electron-withdrawing anions can be sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, or mixtures thereof, or combinationsthereof. An electron-withdrawing anion can be fluoride, chloride,bromide, phosphate, triflate, bisulfate, or sulfate, or combinationsthereof. In at least one embodiment, the electron-withdrawing anion issulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, or combinations thereof.

Thus, for example, the support material suitable for use in the catalystsystems of the present disclosure can be one or more of fluoridedalumina, chlorided alumina, bromided alumina, sulfated alumina,fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, or combinations thereof. In at least one embodiment, theactivator-support can be, or can include, fluorided alumina, sulfatedalumina, fluorided silica-alumina, sulfated silica-alumina, fluoridedsilica-coated alumina, sulfated silica-coated alumina, phosphatedsilica-coated alumina, or combinations thereof. In another embodiment,the support material includes alumina treated with hexafluorotitanicacid, silica-coated alumina treated with hexafluorotitanic acid,silica-alumina treated with hexafluorozirconic acid, silica-aluminatreated with trifluoroacetic acid, fluorided boria-alumina, silicatreated with tetrafluoroboric acid, alumina treated withtetrafluoroboric acid, alumina treated with hexafluorophosphoric acid,or combinations thereof. Furthermore, the activator-supports optionallycan be treated with a metal ion.

Nonlimiting examples of cations suitable for use in the presentdisclosure in the salt of the electron-withdrawing anion includeammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkylphosphonium, H+, [H(OEt₂)₂]+, or combinations thereof.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the support material. Combinations of electron-withdrawingcomponents can be contacted with the support material simultaneously orindividually, and in any suitable order to provide a chemically-treatedsupport material acidity. For example, in at least one embodiment, twoor more electron-withdrawing anion source compounds in two or moreseparate contacting steps.

In at least one embodiment of the present disclosure, one example of aprocess by which a chemically-treated support material is prepared is asfollows: a selected support material, or combination of supportmaterials, can be contacted with a first electron-withdrawing anionsource compound to form a first mixture; such first mixture can becalcined and then contacted with a second electron-withdrawing anionsource compound to form a second mixture; the second mixture can then becalcined to form a treated support material. In such a process, thefirst and second electron-withdrawing anion source compounds can beeither the same or different compounds.

The method by which the oxide is contacted with the electron-withdrawingcomponent, typically a salt or an acid of an electron-withdrawing anion,can include gelling, co-gelling, impregnation of one compound ontoanother, or combinations thereof. Following a contacting method, thecontacted mixture of the support material, electron-withdrawing anion,and optional metal ion, can be calcined.

According to another embodiment of the present disclosure, the supportmaterial can be treated by a process including: (i) contacting a supportmaterial with a first electron-withdrawing anion source compound to forma first mixture; (ii) calcining the first mixture to produce a calcinedfirst mixture; (iii) contacting the calcined first mixture with a secondelectron-withdrawing anion source compound to form a second mixture; and(iv) calcining the second mixture to form the treated support material.

Polymerization Processes

The present disclosure relates to polymerization processes where monomer(e.g., ethylene; propylene), and optionally comonomer, are contactedwith a catalyst system including an activator and at least one catalystcompound, as described above. The catalyst compound and activator may becombined in any suitable order. The catalyst compound and activator maybe combined prior to contacting with the monomer. Alternatively thecatalyst compound and activator may be introduced into thepolymerization reactor separately, where they subsequently react to formthe active catalyst.

Monomers may include substituted or unsubstituted C₂ to C₄₀ alphaolefins, such as C₂ to C₂₀ alpha olefins, such as C₂ to C₁₂ alphaolefins, such as ethylene, propylene, butene, pentene, hexene, heptene,octene, nonene, decene, undecene, dodecene and isomers thereof. In atleast one embodiment, the monomer includes ethylene and an optionalcomonomer including one or more C₃ to C₄₀ olefins, such as C₄ to C₂₀olefins, such as C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may belinear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and or one or more functional groups. In anotherembodiment, the monomer includes propylene and an optional comonomerincluding one or more ethylene or C₄ to C₄₀ olefins, such as C₄ to C₂₀olefins, such as C₆ to C₁₂ olefins. The C₄ to C₄₀ olefin monomers may belinear, branched, or cyclic. The C₄ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and or one or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers may includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbomene, ethylidenenorbornene,vinylnorbornene, norbornadiene, dicyclopentadiene, cyclopentene,cycloheptene, cyclooctene, cyclooctadiene, cyclododecene,7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof,and isomers thereof, such as hexene, heptene, octene, nonene, decene,dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene,1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene,dicyclopentadiene, norbomene, norbomadiene, and their respectivehomologs and derivatives, such as norbomene, norbornadiene, anddicyclopentadiene.

Polymerization processes of the present disclosure can be carried out inany suitable manner. Any suitable suspension, homogeneous, bulk,solution, slurry, or gas phase polymerization process can be used. Suchprocesses can be run in a batch, semi-batch, or continuous mode.Homogeneous polymerization processes and slurry processes can be used. Abulk homogeneous process can be used. Alternately, no solvent or diluentis present or added in the reaction medium, (except for the smallamounts used as the carrier for the catalyst system or other additives,or amounts found with the monomer; e.g., propane in propylene). Inanother embodiment, the process is a slurry process. The term “slurrypolymerization process” means a polymerization process where a supportedcatalyst is employed and monomers are polymerized on the supportedcatalyst particles. At least 95 wt % of polymer products derived fromthe supported catalyst are in granular form as solid particles (notdissolved in the diluent).

Suitable diluents/solvents for polymerization may includenon-coordinating, inert liquids. Examples of diluents/solvents forpolymerization may include straight and branched-chain hydrocarbons,such as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof, such as can be foundcommercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄ to C₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents may also include liquidolefins which may act as monomers or comonomers including ethylene,propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In atleast one embodiment, aliphatic hydrocarbon solvents are used as thesolvent, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof. In anotherembodiment, the solvent is not aromatic, such as aromatics are presentin the solvent at less than 1 wt %, such as less than 0.5 wt %, such asless than 0 wt % based upon the weight of the solvents.

In at least one embodiment, the feed concentration of the monomers andcomonomers for the polymerization is 60 vol % solvent or less, such as40 vol % or less, such as 20 vol % or less, based on the total volume ofthe feedstream. In at least one embodiment, the polymerization is run ina bulk process.

Polymerizations can be run at any suitable temperature and or pressureto obtain a desired polyolefin. Suitable temperatures and or pressuresinclude a temperature of from about 0° C. to about 300° C., such asabout 20° C. to about 200° C., such as about 35° C. to about 160° C.,such as from about 80° C. to about 160° C., such as from about 90° C. toabout 140° C. Polymerizations can be run at a pressure of from about 0.1MPa to about 25 MPa, such as from about 0.45 MPa to about 6 MPa, or fromabout 0.5 MPa to about 4 MPa.

In a suitable polymerization, the run time of the reaction can be up to300 minutes, such as from about 5 minutes to 250 minutes, such as fromabout 10 minutes to 120 minutes, such as from about 20 minutes to 90minutes, such as from about 30 minutes to 60 minutes. In a continuousprocess the run time may be the average residence time of the reactor.In at least one embodiment, the run time of the reaction is from about 5minutes to about 25 minutes.

In at least one embodiment, hydrogen is present in the polymerizationreactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345kPa), such as from 0.01 psig to 25 psig (0.07 kPa to 172 kPa), such asfrom 0.1 psig to 10 psig (0.7 kPa to 70 kPa).

In at least one embodiment, little or no alumoxane is used in theprocess to produce the polymers. For example, alumoxane can be presentat zero mol %, alternately the alumoxane can be present at a molar ratioof aluminum to transition metal less than 500:1, such as less than300:1, such as less than 100:1, such as less than 1:1.

In at least one embodiment, the polymerization: 1) is conducted attemperatures of 0° C. to 300° C. (such as 25° C. to 250° C., such as 80°C. to 160° C., such as 100° C. to 140° C.); 2) is conducted at apressure of atmospheric pressure to 10 MPa (such as 0.35 MPa to 10 MPa,such as from 0.45 MPa to 6 MPa, such as from 0.5 MPa to 4 MPa); 3) isconducted in an aliphatic hydrocarbon solvent (such as isobutane,butane, pentane, isopentane, hexanes, isohexane, heptane, octane,dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, suchas cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, andmixtures thereof; such as where aromatics are present in the solvent atless than 1 wt %, such as less than 0.5 wt %, such as at 0 wt % basedupon the weight of the solvents); 4) where the catalyst system used inthe polymerization includes less than 0.5 mol %, such as 0 mol %alumoxane, alternately the alumoxane is present at a molar ratio ofaluminum to transition metal less than 500:1, such as less than 300:1,such as less than 100:1, such as less than 1:1; 5) the polymerizationoccurs in one reaction zone; 6) optionally scavengers (such as trialkylaluminum compounds) are absent (e.g., present at zero mol %, alternatelythe scavenger is present at a molar ratio of scavenger metal totransition metal of less than 100:1, such as less than 50:1, such asless than 15:1, such as less than 10:1); and 7) optionally hydrogen ispresent in the polymerization reactor at a partial pressure of 0.001psig to 50 psig (0.007 kPa to 345 kPa) (such as from 0.01 psig to 25psig (0.07 kPa to 172 kPa), such as 0.1 psig to 10 psig (0.7 kPa to 70kPa)). In at least one embodiment, the catalyst system used in thepolymerization includes no more than one catalyst compound. A “reactionzone” also referred to as a “polymerization zone” is a vessel wherepolymerization takes place, for example a stirred-tank reactor or a loopreactor. When multiple reactors are used in a continuous polymerizationprocess, each reactor is considered as a separate polymerization zone.For a multi-stage polymerization in a batch polymerization process, eachpolymerization stage is considered as a separate polymerization zone. Inat least one embodiment, the polymerization occurs in one reaction zone.Room temperature is 23° C. unless otherwise noted.

In at least one embodiment, the present disclosure provides a processfor the production of an ethylene based polymer including: polymerizingethylene by contacting the ethylene with the catalyst system of thepresent disclosure described above in one or more continuous stirredtank reactors or loop reactors, in series or in parallel, at a reactorpressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from30° C. to 230° C. to form an ethylene based polymer. In at least oneembodiment, hydrogen is present in the polymerization reactor at apartial pressure of from about 5 psig to about 300 psig, such as fromabout 10 psig to about 250 psig, such as from about 30 psig to about 200psig, such as from about 20 psig to about 150 psig, such as from about50 psig to about 100 psig (e.g., 75 psig).

In another embodiment, the present disclosure provides a process for theproduction of propylene based polymer including: polymerizing propyleneby contacting the propylene with the catalyst system of the presentdisclosure described above in one or more continuous stirred tankreactors or loop reactors, in series or in parallel, at a reactorpressure of from 0.5 MPa to 1,500 MPa and a reactor temperature of from30° C. to 230° C. to form a propylene based polymer. In at least oneembodiment, hydrogen is present in the polymerization reactor at apartial pressure from about 10 psig to about 300 psig, such as fromabout 20 psig to about 250 psig, such as from about 30 psig to about 200psig, such as from about 40 psig to about 150 psig, such as from about50 psig to about 100 psig (e.g., 75 psig).

In another embodiment, the present disclosure provides a process for theproduction of an ethylene alpha-olefin copolymer including: polymerizingethylene and at least one C₃-C₂₀ alpha-olefin (e.g., hexene) bycontacting the ethylene and the at least one C₃-C₂₀ alpha-olefin (e.g.,hexene) with a catalyst system described above in one or more continuousstirred tank reactors or loop reactors, in series or in parallel, at areactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperatureof from 30° C. to 230° C. to form an ethylene alpha-olefin copolymer. Inat least one embodiment, hydrogen is present in the polymerizationreactor at a partial pressure of from about 10 psig to about 300 psig,such as from about 20 psig to about 250 psig, such as from about 30 psigto about 200 psig, such as from about 40 psig to about 150 psig, such asfrom about 50 psig to about 100 psig (e.g., 75 psig), alternatively fromabout 150 psig to about 300 psig (e.g., 200 psig).

In at least one embodiment, a process for the production of an ethylenealpha-olefin copolymer includes: polymerizing ethylene and at least oneC₃-C₂₀ alpha-olefin by contacting the ethylene and the at least oneC₃-C₂₀ alpha-olefin with catalyst system described above in at least onegas phase reactor at a reactor pressure of from 0.7 bar to 70 bar (e.g.,17 bar) and a reactor temperature of from 20° C. to 150° C., such asfrom 50° C. to 120° C., such as from 70° C. to 110° C. (e.g., 85° C.) toform an ethylene alpha-olefin copolymer.

In another embodiment, the present disclosure provides a process for theproduction of a propylene alpha-olefin copolymer including: polymerizingpropylene and at least one ethylene and or at least one C₄-C₂₀alpha-olefin by contacting the propylene and the at least one ethyleneand or at least one C₃-C₂₀ alpha-olefin with a catalyst system describedabove in one or more continuous stirred tank reactors or loop reactors,in series or in parallel, at a reactor pressure of from 0.05 MPa to1,500 MPa and a reactor temperature of from 30° C. to 230° C. to form anethylene alpha-olefin copolymer. In at least one embodiment, hydrogen ispresent in the polymerization reactor at a partial pressure of fromabout 10 psig to about 300 psig, such as from about 20 psig to about 250psig, such as from about 30 psig to about 200 psig, such as from about40 psig to about 150 psig, such as from about 50 psig to about 100 psig(e.g., 75 psig), alternatively from about 150 psig to about 300 psig(e.g., 200 psig).

In at least one embodiment, the conversion of olefin monomer is at least10%, based upon polymer yield and the weight of the monomer entering thereaction zone, such as 20% or more, such as 30% or more, such as 50% ormore, such as 80% or more.

In at least one embodiment, little or no alumoxane is used in theprocess to produce the polymers. For example, alumoxane is present atzero mol %, alternately the alumoxane is present at a molar ratio ofaluminum to transition metal less than 500:1, such as less than 300:1,such as less than 100:1, such as less than 1:1.

In at least one embodiment, little or no scavenger is used in theprocess to produce the ethylene polymer. For example, scavenger (such astri alkyl aluminum) is present at zero mol %, alternately the scavengeris present at a molar ratio of scavenger metal to transition metal ofless than 100:1, such as less than 50:1, such as less than 15:1, such asless than 10:1.

Other additives may optionally be used in the polymerization, such asone or more scavengers, hydrogen, aluminum alkyls, or chain transferagents (such as alkylalumoxanes, a compound represented by the formulaAlR₃ or ZnR₂ (where each R is, independently, a C₁-C₈ aliphatic radical,such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomerthereof) or a combination thereof, such as diethyl zinc,methylalumoxane, trimethylaluminum, triisobutylaluminum,trioctylaluminum, or a combination thereof).

Solution Polymerization

A solution polymerization is a polymerization process in which thepolymer is dissolved in a liquid polymerization medium, such as an inertsolvent or monomer(s) or their blends. A solution polymerization istypically homogeneous. A homogeneous polymerization is one where thepolymer product is dissolved in the polymerization medium. Such systemsare not turbid as described in J. Vladimir Oliveira, C. Dariva and J. C.Pinto, Ind. Eng, Chem. Res. 29, 2000, 4627. Solution polymerization mayinvolve polymerization in a continuous reactor in which the polymerformed, the starting monomer and catalyst materials supplied areagitated to reduce or avoid concentration gradients and in which themonomer acts as a diluent or solvent or in which a hydrocarbon is usedas a diluent or solvent. Suitable processes can operate at temperaturesfrom about 0° C. to about 250° C., such as from about 50° C. to about170° C., such as from about 80° C. to about 150° C., such as from about100° C. to about 140° C., and or at pressures of about 0.1 MPa or more,such as 2 MPa or more. The upper pressure value is not criticallyconstrained but can be about 200 MPa or less, such as 120 MPa or less,such as 30 MPa or less. Temperature control in the reactor can typicallybe obtained by balancing the heat of polymerization and with reactorcooling by reactor jackets or cooling coils to cool the contents of thereactor, auto refrigeration, pre-chilled feeds, vaporization of liquidmedium (diluent, monomers or solvent) or combinations of all three.Adiabatic reactors with pre-chilled feeds can also be used. The purity,type, and amount of solvent can be adjusted for improved catalystproductivity for a particular type of polymerization. The solvent can bealso introduced as a catalyst carrier. The solvent can be introduced asa gas phase or as a liquid phase depending on the pressure andtemperature. Advantageously, the solvent can be kept in the liquid phaseand introduced as a liquid. Solvent can be introduced in the feed to thepolymerization reactors.

A polymerization process can be a solution polymerization process thatmay be performed in a batchwise fashion (e.g., batch; semi-batch) or ina continuous process. Suitable reactors may include tank, loop, and tubedesigns. In at least one embodiment, the process is performed in acontinuous fashion and dual loop reactors in a series configuration areused. In at least one embodiment, the process is performed in acontinuous fashion and dual continuous stirred-tank reactors (CSTRs) ina series configuration are used.

Furthermore, the process can be performed in a continuous fashion and atube reactor can be used. In another embodiment, the process isperformed in a continuous fashion and one loop reactor and one CSTR areused in a series configuration. The process can also be performed in abatchwise fashion and a single stirred tank reactor can be used.

Other Embodiments of the Present Disclosure

Clause 1. A method for introducing an activator to a polymerizationreactor comprising:

introducing an amount of liquid activator to a mixing vessel;

mixing an aliphatic hydrocarbon solvent with the liquid activator in themixing vessel to form an activator solution; and

introducing the activator solution to a polymerization reactor.

Clause 2. The method of clause 1, further comprising pumping theactivator solution from the mixing vessel to the polymerization reactor.

Clause 3. The method of any of clauses 1, further comprising introducingthe activator solution to a charge vessel before the introducing theactivator solution to a polymerization reactor.

Clause 4. The method of clause 3, further comprising pumping theactivator solution from the charge vessel to the polymerization reactor.

Clause 5. The method of any of clauses 1 to 4, further comprisingmeasuring the amount of liquid activator entering the mixing vessel.

Clause 6. The method of clause 5, wherein the measuring of the amount ofliquid activator is accomplished by use of a flowmeter in a lineconnecting a storage tank to the mixing vessel.

Clause 7. The method of clause 5, wherein the measuring of the amount ofliquid activator is accomplished by use of a metering valve in a lineconnecting a storage tank to the mixing vessel.

Clause 8. The method of any of clauses 1 to 7, further comprisingmeasuring the amount of aliphatic hydrocarbon entering the mixingvessel.

Clause 9. A method for introducing an activator to a polymerizationreactor comprising:

introducing an amount of liquid activator to an inline mixer;

mixing an aliphatic hydrocarbon solvent with the liquid activator in theinline mixer to form an activator solution; and

introducing the activator solution to a polymerization reactor.

Clause 10. The method of clause 9, further comprising pumping theactivator solution from the inline mixer to the polymerization reactor.

Clause 11. The method of clause 9, further comprising introducing theactivator solution to a charge vessel before the introducing theactivator solution to a polymerization reactor.

Clause 12. The method of clause 11, further comprising pumping theactivator solution from the charge vessel to the polymerization reactor.

Clause 13. The method of any of clauses 9 to 12, further comprisingmeasuring the amount of liquid activator entering the inline mixer.

Clause 14. The method of clause 13, wherein the measuring of the amountof liquid activator is accomplished by use of a flowmeter in a lineconnecting a storage tank to the inline mixer.

Clause 15. The method of clause 13, wherein the measuring of the amountof liquid activator is accomplished by use of a metering valve in a lineconnecting a storage tank to the inline mixer.

Clause 16. The method of any of clauses 9 to 15, further comprisingmeasuring the amount of aliphatic hydrocarbon entering the inline mixer.

Clause 17. A system for introducing an activator to a polymerizationreactor comprising:

a storage vessel;

a mixing vessel configured to mix a liquid activator and aliphatichydrocarbon solvent, wherein the mixing vessel is fluidly connected withthe storage vessel; and

a polymerization reactor fluidly connected with the mixing vessel.

Clause 18. The system of clause 17, further comprising a charge vesselfluidly connected with the mixing vessel and the polymerization reactor.

Clause 19. The system of any of clauses 17 to 18, further comprising ametered valve configured to measure an amount of activator introduced tothe mixing vessel.

Clause 20. The system of any of clauses 17 to 19, further comprising ametered valve configured to measure an amount of aliphatic hydrocarbonsolvent introduced to the mixing vessel.

Clause 21. A system for introducing an activator to a polymerizationreactor comprising:

a storage vessel;

an inline mixer configured to mix a liquid activator and aliphatichydrocarbon solvent, wherein the inline mixer is fluidly connected withthe storage vessel; and

a polymerization reactor fluidly connected with the inline mixer.

Clause 22. The system of clause 21, further comprising a charge vesselfluidly connected with the inline mixer and the polymerization reactor.

Clause 23. The system of any of clauses 21 to 22, further comprising ametered valve configured to measure an amount of activator introduced tothe inline mixer.

Clause 24. The system of any of clauses 21 to 23, further comprising ametered valve configured to measure an amount of aliphatic hydrocarbonsolvent introduced to the inline mixer.

Clause 25. A method for introducing an activator to a polymerizationreactor comprising:

introducing an amount of aliphatic hydrocarbon solvent to an amount ofliquid activator in a vessel to form an activator solution; and

introducing the activator solution to a polymerization reactor.

Clause 26. A process for producing a polyolefin, the process comprising:

introducing an amount of liquid activator to an inline mixer;

mixing an aliphatic hydrocarbon solvent with the liquid activator in theinline mixer to form an activator solution; and

introducing the activator solution, a catalyst, and an olefin feed to apolymerization reactor.

Clause 27. The process of clause 26, wherein the liquid activator has adensity of about 0.8 g/ml.

Overall, it has been discovered that liquid activators for olefinpolymerization may be prepared and introduced to a polymerizationreactor in fewer vessels and with greater control over the quantitiesintroduced as compared to conventional polymerization processes. The useof fewer vessels and lines permits a cost savings in installation andmaintenance and also creates a system less prone to errors whether humanor mechanical. Furthermore, the dissolution and metered introduction ofliquid activators allows for precision in dispensing amounts ofactivator relative to the amount of catalyst used.

While the present disclosure has been described with respect to a numberof embodiments and examples, those skilled in the art, having benefit ofthis disclosure, will appreciate that other embodiments can be devisedwhich do not depart from the scope and spirit of the present disclosure.Furthermore, in some embodiments, the systems and processes of thepresent disclosure may suitably be practiced in the absence of anyelement which is not specifically disclosed.

What is claimed is:
 1. A method for introducing an activator to apolymerization reactor comprising: introducing an amount of liquidactivator to a mixing vessel; mixing an aliphatic hydrocarbon solventwith the liquid activator in the mixing vessel to form an activatorsolution; and introducing the activator solution to a polymerizationreactor.
 2. The method of claim 1, further comprising pumping theactivator solution from the mixing vessel to the polymerization reactor.3. The method of claim 1, further comprising introducing the activatorsolution to a charge vessel before the introducing the activatorsolution to a polymerization reactor.
 4. The method of claim 3, furthercomprising pumping the activator solution from the charge vessel to thepolymerization reactor.
 5. The method of claim 1, further comprisingmeasuring the amount of liquid activator entering the mixing vessel. 6.The method of claim 5, wherein the measuring of the amount of liquidactivator is accomplished by use of a flowmeter in a line connecting astorage tank to the mixing vessel.
 7. The method of claim 5, wherein themeasuring of the amount of liquid activator is accomplished by use of ametering valve in a line connecting a storage tank to the mixing vessel.8. The method of claim 1, further comprising measuring the amount ofaliphatic hydrocarbon entering the mixing vessel.
 9. The method of claim1, wherein aromatics are present at less than 1 wt %, based upon thetotal weight of solvent in the activator solution.
 10. The method ofclaim 1, wherein the mixing vessel is an inline mixer.
 11. A system forintroducing an activator to a polymerization reactor comprising: astorage vessel; a mixing vessel configured to mix a liquid activator andaliphatic hydrocarbon solvent, wherein the mixing vessel is coupled withthe storage vessel; and a polymerization reactor fluidly connected withthe mixing vessel.
 12. The system of claim 11, further comprising acharge vessel fluidly connected with the mixing vessel and thepolymerization reactor.
 13. The system of claim 11, further comprising ametered valve configured to measure an amount of activator introduced tothe mixing vessel.
 14. The system of claim 11, further comprising ametered valve configured to measure an amount of aliphatic hydrocarbonsolvent introduced to the mixing vessel.
 15. A system for introducing anactivator to a polymerization reactor comprising: a storage vessel; aninline mixer configured to mix a liquid activator and aliphatichydrocarbon solvent, wherein the inline mixer is fluidly connected withthe storage vessel; and a polymerization reactor fluidly connected withthe inline mixer.
 16. The system of claim 15, further comprising acharge vessel fluidly connected with the inline mixer and thepolymerization reactor.
 17. The system of claim 15, further comprising ametered valve configured to measure an amount of activator introduced tothe inline mixer.
 18. The system of claim 15, further comprising ametered valve configured to measure an amount of aliphatic hydrocarbonsolvent introduced to the inline mixer.
 19. The process of claim 1,wherein the liquid activator has a density of about 0.8 g/ml.
 20. Theprocess of claim 1, wherein aromatics are present at less than 1 wt %,based upon the total weight of solvent in the activator solution.